Solvent-free enyne metathesis polymerization

ABSTRACT

The disclosure describes methods of metathesizing unsaturated organic compounds, each method comprising contacting at least one feedstock comprising at least one olefinic or acetylenic precursor with a solid transition metal-based metathesis catalyst in the absence of a liquid solvent or precursor to form a polymer product.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application Ser.No. 61/678,484, filed Aug. 1, 2012, which is incorporated by referencein its entirety.

TECHNICAL FIELD

The present invention relates to polymer-forming metathesis reactionscatalyzed by organometallic coordination compounds. The presentinvention also relates to ruthenium phosphine complexes.

BACKGROUND

Olefin metathesis is a useful tool in preparing a range of polymeric andnon-polymeric intermediates and products for products ranging frompharmaceuticals to organic semiconductors. In part, due to theefficiency of the available catalysts, current synthetic methods forpreparing discrete, non-polymeric compounds are generally accomplishedusing solution-based systems. Polymers may also be prepared usingsolution-based systems, but more recently, experimentalists have alsoused methods using vapor phase reactions. The reaction conditionsassociated with such reactions—sublimation or vapor phase liquidtransfer—results in conditions where localized condensation occurs atthe site of catalytic activity. These localized solvent effects giverise to variation of growth rates, orientations of individual polymerstrands within an array of growing polymers, or both. In certainapplications, for example in organic semiconductor devices, reducingsuch variability is important for more consistent performance. Thepresent invention is directed to addressing one or more of theaforementioned concerns.

SUMMARY

The present inventions are directed to methods of metathesizingunsaturated organic compounds, each method comprising contacting atleast one feedstock vapor or gas comprising at least one olefinic oracetylenic precursor with a solid transition metal-based metathesiscatalyst to form a polymer product, wherein the transition metal-basedmetathesis catalyst is in a solid form and the contacting is done in theabsence of a liquid. In specific independent embodiments, the methodsemploy direct gas/solid phase polymerization reactions, avoiding thepresence of bulk or localized liquids at the site of catalytic activity,and the product polymer is formed by an enyne, diyne, or ring openingmetathesis polymerization (ROMP) reaction. The methods may be operableat near ambient conditions, using a range of metathesis catalysts,including various versions of the Grubbs' catalysts.

In addition to the methods, the inventions are directed to thecompositions which result from operating the inventive methods. Thesecompositions may be free-standing polymer-containing compositions orcompositions in which the polymer is attached, or tethered, to asurface. This disclosure further described devices derived from suchmethods and compositions, for example, polymer electronic devices (e.g.diodes, capacitors, chemical sensors, light emitting diodes (LEDs),photodetectors, photovoltaic cells, thermoelectric detectors, ortransistors), medical implants, composite materials, antireflectioncoatings, antifouling coatings, microfluidics, and reactor modificationfor chemical synthesis.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods, devices, and systems disclosed. Inaddition, the drawings are not necessarily drawn to scale. In thedrawings:

FIG. 1 provides an illustration of the proposed mechanism describedspecifically in Example 3.

FIG. 2 shows a micrograph of a sample prepared as described in Example3.

FIG. 3A provides an illustration of the structure of the device preparedin Example 4.

FIG. 3B illustrates the energy levels before equilibration (not incontact) of the three constituent materials of Example 4. The proposedeffect of the dipole of a Self-Assembled Monolayer of Phosphonate (SAMP)is shown. This is designed to lower the work function of the Alelectrode to above the electron affinity of polyacetylene, to accessinversion.

FIG. 3C shows the relationship between current and applied voltage forthe device prepared in Example 4.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, conditions or parameters described or shown herein, and thatthe terminology used herein is for the purpose of describing particularembodiments by way of example only and is not intended to be limiting ofany claimed invention. Similarly, unless specifically otherwise stated,any description as to a possible mechanism or mode of action or reasonfor improvement is meant to be illustrative only, and the inventionherein is not to be constrained by the correctness or incorrectness ofany such suggested mechanism or mode of action or reason forimprovement. Throughout this text, it is recognized that thedescriptions refer to compositions and methods of making and using saidcompositions. That is, where the disclosure describes or claims afeature or embodiment associated with a composition or a method ofmaking or using a composition, it is appreciated that such a descriptionor claim is intended to extend these features or embodiment toembodiments in each of these contexts (i.e., compositions, methods ofmaking, and methods of using).

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. In general, use of the term “about” indicates approximationsthat can vary depending on the desired properties sought to be obtainedby the disclosed subject matter and is to be interpreted in the specificcontext in which it is used, based on its function. The person skilledin the art will be able to interpret this as a matter of routine. Insome cases, the number of significant figures used for a particularvalue may be one non-limiting method of determining the extent of theword “about.” In other cases, the gradations used in a series of valuesmay be used to determine the intended range available to the term“about” for each value. Where present, all ranges are inclusive andcombinable. That is, references to values stated in ranges include everyvalue within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of,” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method steps; (ii) “consisting of” excludes any element,step, or ingredient not specified in the claim; and (iii) “consistingessentially of” limits the scope of a claim to the specified materialsor steps “and those that do not materially affect the basic and novelcharacteristic(s)” of the claimed invention. Embodiments described interms of the phrase “comprising” (or its equivalents), also provide, asembodiments, those which are independently described in terms of“consisting of” and “consisting essentially” of For those embodimentsprovided in terms of “consisting essentially of,” the basic and novelcharacteristic(s) is the operability of the methods (or the compositionsor devices derived therefrom) as a direct gas/solid phase reaction.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C.”

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

The present invention includes embodiments related to methods ofmetathesizing olefinic or acetylenic precursors using transitionmetal-based metathesis catalysts and the products deriving from suchmethods, and devices made from such products. Among the embodiments ofthe present invention are methods of metathesizing unsaturated organiccompounds, each method comprising contacting at least one feedstockvapor or gas comprising at least one olefinic or acetylenic precursorwith a solid transition metal-based metathesis catalyst to form apolymer product, wherein the transition metal-based metathesis catalystis in a solid form (i.e., undissolved in a solvent or liquid precursor)and the contacting is done in the absence of a liquid (including solventor precursor). That is, as contemplated herein, such that the olefinicor acetylenic precursor is presented to the solid transition metal-basedmetathesis catalyst as a vapor or gas. As used herein, the terms “gas”and “vapor” are distinguished, in that the term “gas” is used todescribe a condition where the partial pressure of the precursor organiccompound is less than the saturated vapor pressure for that material atthe conditions applied during the polymerization reaction, whereas theterm “vapor” refers to a condition where the precursor compound is at orabove the saturated vapor pressure at the conditions applied for themetathesis. Separate additional independent embodiments provide that theterm gas refers to a condition wherein the partial pressure of precursorcompound is in a range having a lower value of about 0.001%, about0.01%, about 0.1%, about 1%, 5%, about 10%, about 25%, or about 50% andan upper value of about 99%, about 95%, about 90%, about 80%, about 75%,about 50%, about 25%, about 10%, about 5%, about 2%, or about 1% of thesaturated vapor pressure for that material at the conditions appliedduring the polymerization reaction. Exemplary, non-limiting, rangesinclude from about 0.1% to about 1%, from about 1% to about 5%, from 1%to about 10%, from about 5% to about 10%, and from about 5% to about25%, of the saturated vapor pressure for that material at the conditionsapplied during the polymerization reaction. Accordingly, reactionsinvolving subliming solids, or other reaction conditions wherein thevolatilized precursor compound are in equilibrium with its correspondingsolid or liquid phase are considered to involve vapor phase, and not gasphase, conditions. The term “gas” is also intended to include thosematerials at conditions above their critical points—i.e., supercriticalconditions. The direct vapor/solid phase and direct gas/solid phasepolymerization reactions are considered to be independent variants ofthe general invention. While both are considered within the scope of thepresent disclosure, direct gas/solid phase polymerization reactions arepreferred. To the knowledge of the inventors, at least the directgas/solid phase polymerization reactions described herein areunprecedented using metathesis catalysts.

Also, and as will become apparent during the following discussion, andwhile not intending to be bound by the correctness of the theorydescribed herein, the technology may be envisioned in terms that thegrowing polymer material is comprised of an individual polymer chain oran array of polymer chains with a living layer of catalyst at thesurface (or at the “distal ends” of the “growing” polymer chains). Whilenot requiring that the growing polymer(s) is/are attached to anysurface, one advantage of such a phenomenon, is that it enablesimprinting of a surface pattern/texture/etc. (either physisorbed orchemically tethered) onto the material being grown. It also enables theliving catalyst layer at the surface to be used for furtherfunctionality (e.g., in making blocks for block copolymers, recyclingthe catalyst, and in transforming the catalyst to make functionalized orfurther active termini) This is very much distinguished from asolution-phase reaction, or even a vapor phase reaction, where solvationleads to a greater degree of reorganization/diffusion of the livingcatalyst species—and thus randomization (loss of surface “memory”) ofthe polymer material being grown.

Returning again to some embodiments of the invention, and as describedabove, each method comprises contacting at least one feedstock vapor orgas comprising at least one olefinic or acetylenic precursor with asolid transition metal-based metathesis catalyst to form a polymerproduct, wherein the transition metal-based metathesis catalyst is in asolid form and the contacting is done under direct vapor/solid phase anddirect gas/solid phase polymerization reaction conditions. In certainembodiments, the product polymer is formed by a mechanism comprising anenyne reaction, a diyne reaction, a ring opening metathesispolymerization (ROMP) reaction, or a combination or each type ofreaction, though it should be appreciated that the teachings describedherein may be applied to and incorporate other types of metathesisreactions (e.g., cross metathesis reactions). In preferred embodiments,the method provides that the product polymer results from at leastpartial polymerization of an acetylene (especially acetylene itself) byan enyne (or diyne) mechanism. That is, the methods provide for directgas/solid phase polymerization reactions incorporating acetylenicprecursors into either random or block copolymers, along with othernon-acetylenic precursors. For example, certain independent embodimentsprovide that at least one of the feedstocks may independently compriseat least one olefinic precursor, or at least one acetylenic precursor,or a mixture of one or more olefinic and acetylenic precursors. Otherembodiments provide that the product polymer may derive from applicationof a singly applied feedstock or a plurality of feedstocks appliedsequentially. That is, the polymerization can be paused by reducing theamount of available feedstock precursors, eliminating free feedstockprecursors, or transferring the polymerization to a new environment. Thepolymerization can be resumed by reintroducing the same or differentfeedstock precursors to the previously formed polymer chains. Similarly,the polymerization can be stopped by exposing the polymer chains to achain transfer agent. Chain transfer agents transfer the catalyst from agrowing polymer chain to the chain transfer agent. Since thepolymerization occurs at the terminal, distal end of the polymerchain(s), the use of a chain transfer agent results in all or a portionof the chain transfer agent being bonded to the end to the polymerchains. This enables one to functionalize the terminal, distal ends ofthe growing polymer strands and, where present as a plurality of polymerstrands, the surface of the polymeric material. Illustrativefunctionalized chain transfer agents include those represented by ageneral formula X—CH═CH—Y, where X and Y may be the same or different.These chain transfer agents may include, but are not limited to,symmetrical internal olefins or vinyl ethers. These chain transferagents may also be optionally substituted, such as substituted with anamino, carbene, carboxylate, catecholate, a dithiocarbamate, dithioicacid, hydroxy, hydroxyamic acid, isocyanato, nitrite, phosphate,phosphonate, a silane or silicate, or thiol groups, or any combinationthereof.

The skilled artisan would appreciate the various types of polymerclasses that such options present. For example, application of a singlefeedstock would results in a homopolymer derived from the monomers ofthat precursor; e.g., where only acetylene is used, the product polymerwould be polyacetylene. In another example, application of a singlefeedstock comprising a mixture of at least one olefinic precursor, or atleast one acetylenic precursor, or a mixture of one or more olefinic andacetylenic precursors would result in either a random copolymer, apartial block copolymer, or a pure block copolymer, the exact nature ofwhich depending on the relative concentrations and reactivities of therespective monomer precursors. In yet another application, sequentialapplications of individual feedstocks comprising, for example, anolefinic precursor, an acetylenic precursor, and a different acetylenicprecursor would result in a deliberately engineered block copolymer. Inthose cases where multiple steps are involved, it is not necessary thatevery application employs the inventive steps described herein to beconsidered within the scope of the present invention, so long as oneapplication does. These examples are not intended to be limiting, butrepresentative of possible options, and again the specific design of theproduct polymers would be within the skill and control of the person ofordinary skill in the art, using the teachings presented here.

As described herein, in certain embodiments, the methods providepolyacetylene polymers or blocks within block co-polymers. Depending onthe choice of reaction conditions, for example temperature, pressure,and choice of catalyst (see, e.g., below), in some of these embodiments,the polyacetylene may form in a substantially cis-conformation (i.e., asa cis-polyacetylene polymer or block) and in other embodiments in asubstantially trans-conformation (i.e., as trans-polyacetylene polymeror block). Similar experimental modifications may be employed to providethat the incorporated olefins adopt similar cis- or trans-conformations.

The methods may use precursors that contain electron donor substituents,electron acceptor substituents, or both, such that the precursor, whenpolymerized, is capable of forming a semiconducting polymer or polymerblock that acts as an electron donor, acceptor, or both. Note that theability to prepare block copolymers comprising separate donor/acceptorblocks offers the possibility of forming p-n junctions to use as diodesand the like. Suitable precursors are those which provide polymers thatare electron acceptors or donors or semiconducting organometallicpolymers that are electron acceptors or electron donors or emitters. Asdescribed herein, these methods can be modified to provide polymers orpolymer blocks that are doped to behave as a p-type semiconductors or ann-type semiconductor. Especially suitable precursors are those which arecapable of providing polyacetylenes, polypyrroles, polyanilines,poly(thienylenevinylene)s, polythiophenes, and poly(phenylenevinylene)s,any of which can be substituted or unsubstituted and branched orunbranched. As describes elsewhere herein, a particularly useful exampleof precursor is acetylene, capable of providing polyacetylenes.

The methods can be used to provide polymer products of virtually anylength, individual embodiments described some such lengths as beingwithin a range having a lower value of about 5 nm, about 10 nm, about 50nm, about 100 nm, about 500 nm, or about 1000 nm and an upper value ofabout 10,000 nm, about 5000 nm, about 1000 nm, about 500 nm, about 100nm, or about 50 nm. Illustrative, non-limiting ranges, then, can includethose from about 10 nm to about 10,000 nm, about 10 nm to 1000 nm, orabout 50 nm to about 500 nm.

Stated differently, the methods can be used to provide polymer products(including polymers or polymer blocks) which are not intrinsicallylimited by the number of repeating units. However, so as to specify somelimits, certain embodiments provide that the methods independentlyprovide polymers or polymer blocks having at least about 5, 50, or 500repeating units, less than 500,000, 50,000, or 5000 repeating units, orany combination thereof.

One of the many advantages of the present invention is that the rate atwhich the different polymer chains grow is more consistent than seen intraditional chain polymerization reactions. The similarity in growthrate for each individual polymer strand results in chains of verysimilar lengths. In separate embodiments, at least about 50%, 60%, 70%,80%, or at least about 90% of the formed product polymer chains havelengths within 50 nm, 25 nm or 10 nm of their average length.

The methods may further comprise steps which comprise co-depositing, orsequentially stepwise depositing nanoparticles or other materials,during or following a metathesis reaction. Unless otherwise specified,nanoparticles include those particles or fibrils having a least onedimension in a range of from about 1 nm to about 1000 nm. Additionalindependent embodiments provide that such particles may have suchparticle dimensions in a range having a lower value of about 1 nm, about2 nm, about 5 nm, about 10 nm, or about 50 nm and an upper value ofabout 1000 nm, about 800 nm, about 600 nm, about 400 nm, about 200 nm,or about 100 nm, with exemplary ranges including those from about 2 nmto about 100 nm, from 2 nm, or from bout to about 50 nm, or a range offrom about 5 nm to about 10 nm. In the context of the present invention,nanoparticles may be organic or inorganic and may include, but are notlimited to, nanotubes, magnetic nanoparticles and quantum dots.

Since, as suggested above, the polymerization can be paused at nearlyany point in the reaction and then resumed, a layer of nanoparticles canoptionally be formed on the partially formed active polymer chains whilethe polymerization is paused. When the polymerization is resumed, theactive polymer chains can extend through interstices in thenanoparticles. The ability to pause the polymerization at nearly anypoint in the polymerization allows one or more layers of thenanoparticles to be positioned anywhere along the length of the activepolymer chains. For instance, a layer of the nanoparticles can bepositioned such that the p-n junctions are positioned in the intersticesof the nanoparticles. Additionally, the nanoparticles can be selected toscatter incident light. When the nanoparticles are positioned to scatterthis light near the p-n junctions, the amount of light absorbed near thep-n junctions can be increased in order to further enhance theefficiency of the device. In addition to scattering light or as analternative to scattering light, the nanoparticles can increase opticaldensity near the nanoparticles as a result of the nanoparticles behavingas an antenna. When the nanoparticles are positioned to enhance lightdensity near the p-n junctions, the amount of light absorbed near thep-n junctions can be increased in order to further enhance theefficiency of the device.

The methods may further comprise steps which comprise co-depositing, orsequentially stepwise depositing other materials during or following ametathesis reaction. Such “other materials” may include species whichmay act as a dopant in the final form product. Iodine is one suchexemplary molecule, having sufficient volatility to be useful in thiscapacity. Similarly, metals or other conductors may be deposited ontothe polymer products.

As described above, among the embodiments of the present invention arethose methods in which the metathesis reactions are described in termsdirect vapor/solid phase and direct gas/solid phase polymerization,preferably the latter. One advantage of the inventive methods is thatthe metatheses can be conducted under miler conditions under relativelymilder conditions, relative the corresponding solvent-based oruncatalyzed reactions. That said, various embodiments include thosewhere the metathesis reaction is carried out under conditions where theat least one olefinic or acetylenic precursor has a partial pressure ina range of from about 0.1 psia to about 300 psia, at a temperature in arange of from about −10° C. to about 300° C., or both. The methods maystill be operable outside of these ranges, though one would expect thatthese conditions would be at the expense of any useful kinetics. Inother independent embodiments, the methods may be practiced at precursorpartial pressures bounded by ranges in which the lower value is about0.1, about 0.5, about 1, about 2, about 3, about 4, about 5, about 6,about 7, about 8, about 9, about 10, about 15, about 20, about 25, about30, about 40, about 50, about 60, about 70, about 80, about 90, or about100 psia and the upper value of the range is about 10, about 20, about30, about 40, about 50, about 60, about 80, about 100, about 120, about140, about 160, about 180, or about 200 psia. Likewise, the methods maybe practiced at temperatures bounded by ranges in which the lower valueis about −10° C., about 0° C., about 20° C., about 40° C., about 60° C.,about 80° C., or about 100° C., and the upper end of the range is about300° C., about 275° C., about 250° C., about 225° C., about 200° C.,about 180° C., about 160° C., about 140° C., about 120° C., about 120°C., or about 100° C. As the skilled artisan will appreciate, the choiceof operating conditions, particularly temperature, will depend on anumber of factors, including the nature of the organic precursors andthe transition metal catalysts, through the skilled artisan would beable to define these without undue experimentation.

Acetylenic Precursors

The methods herein are described in terms of at least one feedstockcomprising at least one olefinic or acetylenic precursor. In principle,these feedstocks may comprise precursors comprising cyclic or alicycliccis- or trans-alkenes or compounds containing an alkyne linkage. Sincemethods employing direct gas/solid phase polymerization reactions arepreferred, those precursors that are sufficiently volatile under thereactions conditions described below as to be present in the gas phase(as contrasted to the vapor phase) are also preferred. Also as suggestedelsewhere herein, given the preference for products accessible by enyneor diyne reaction mechanisms, optionally substituted acetylenes (alkynylcompounds) are particularly suitable, and in some cases necessary,precursors for these methods. Lower alkynyl (acetylenic) compounds areparticularly suitable. As used herein, the term “alkynyl” (or“acetylenic”) or “alkyne” refers to a linear or branched hydrocarbongroup or compound of 2 to about 24 carbon atoms containing at least onetriple bond, such as ethynyl, n-propynyl, and the like. Preferredalkynyl groups herein contain 2 to about 12 carbon atoms, preferablycontaining a terminal alkyne bond. The term “lower alkynyl” refers to analkynyl group of 2 to 6 carbon atoms. The term “substituted alkynyl”refers to alkynyl substituted with one or more substituent groups. Asused herein, the terms “optional” or “optionally” mean that thesubsequently described circumstance may or may not occur, so that thedescription includes instances where the circumstance occurs andinstances where it does not. For example, the phrase “optionallysubstituted” means that a non-hydrogen substituent may or may not bepresent on a given atom, and, thus, the description includes structureswherein a non-hydrogen substituent is present and structures wherein anon-hydrogen substituent is not present.

Acetylene (ethyne) itself is a particularly attractive precursor for thevarious embodiments described herein, but other lower alkynes may alsobe employed, depending on the desired final polymer products. Similarly,aryl substituted alkynes may also be suitable. As will be describedfurther below, anchored or tethered polyacetylenes are attractiveproducts from the inventive methods.

Olefinic Precursors

Olefinic precursors may be used in tandem with the acetylenes, eitheremployed as part of the feedstock mixtures, or in sequential processingof the product polymers. Suitable options for such precursors are thosering systems, particularly strained ring systems, which are useful forROMP reactions. One such class of compounds in this regard issubstituted or unsubstituted cyclooctatetraenes, includingcyclooctatetraene itself. However, a polymer or polymer block derivedfrom this material would be a polyacetylene, and this moiety ispreferably derived in this invention from acetylene itself. Becausecyclooctatetraene is made from acetylene, use of this latter precursorby an enyne reaction offers a more direct, efficient and economicalsynthesis. The ability to operate at the solid/gas interface for thesurface confined polymerization of polyacetylene enables direct controlover the pressure and temperature of the system.

When considering alternative olefinic precursors in the present methods,more preferred precursors may be those which, which when incorporatedinto polyacetylene polymers or copolymers, modify the electrical orphysical character of the resulting polymer. One general class of suchpresursors are substituted annulenes and annulynes, for example[18]annulene-1,4;7,10;13,16-trisulfide. When co-polymerized withacetylene, this precursor can form a block co-polymer as shown here:

Substituted analogs of these trisulfides, as described below can also beused to provide corresponding substitutedpoly(thienylvinylene)-containing polymers or copolymers. For example,the 2,3,8,9,14,15-hexaoctyl derivative of[18]annulene-1,4;7,10;13,16-trisulfide is described in Horie, et al.,“Poly(thienylvinylene) prepared by ring-opening metathesispolymerization: Performance as a donor in bulk heterojunction organicphotovoltaic devices,” Polymer 51 (2010) 1541-1547, which isincorporated by reference herein for all purposes

As described above, suitable options for such olefinic or acetylenicprecursors include ring systems, particularly strained ring systems,which are useful for ROMP reactions. Such cyclic olefins may beoptionally substituted, optionally heteroatom-containing,mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefinmay generally be any strained or unstrained cyclic olefin, provided thecyclic olefin is able to participate in a ROMP reaction eitherindividually or as part of a ROMP cyclic olefin composition. Whilecertain unstrained cyclic olefins such as cyclohexene are generallyunderstood to not undergo ROMP reactions by themselves, underappropriate circumstances, such unstrained cyclic olefins maynonetheless be ROMP active. For example, when present as a co-monomer ina ROMP composition, unstrained cyclic olefins may be ROMP active.Accordingly, as used herein and as would be appreciated by the skilledartisan, the term “unstrained cyclic olefin” is intended to refer tothose unstrained cyclic olefins that may undergo a ROMP reaction underany conditions, or in any ROMP composition, provided the unstrainedcyclic olefin is ROMP active.

In general, the cyclic olefin may be represented by the structure offormula (A)

wherein J, R^(A1), and R^(A2) are as follows:

R^(A1) and R^(A2) is selected independently from the group consisting ofhydrogen, hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl,or C₅-C₃₀ alkaryl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl),heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl), and substitutedheteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl,C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl) and, if substituted hydrocarbyl orsubstituted heteroatom-containing hydrocarbyl, wherein the substituentsmay be functional groups (“Fn”) such as phosphonato, phosphoryl,phosphanyl, phosphino, sulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₀arylsulfanyl, C₁-C₂₀ alkylsulfonyl, C₅-C₂₀ arylsulfonyl, C₁-C₂₀alkylsulfinyl, C₅-C₂₀ arylsulfinyl, sulfonamido, amino, amido, imino,nitro, nitroso, hydroxyl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl, carboxyl, carboxylato, mercapto,formyl, C₁-C₂₀ thioester, cyano, cyanato, thiocyanato, isocyanate,thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl,siloxazanyl, boronato, boryl, or halogen, or a metal-containing ormetalloid-containing group (wherein the metal may be, for example, Sn orGe). R^(A1) and R^(A2) may itself be one of the aforementioned groups,such that the Fn moiety is directly bound to the olefinic carbon atomindicated in the structure. In the latter case, however, the functionalgroup will generally not be directly bound to the olefinic carbonthrough a heteroatom containing one or more lone pairs of electrons,e.g., an oxygen, sulfur, nitrogen, or phosphorus atom, or through anelectron-rich metal or metalloid such as Ge, Sn, As, Sb, Se, Te, etc.With such functional groups, there will normally be an interveninglinkage Z*, such that either or both of R^(A1) and R^(A2) then has thestructure —(Z*)_(n)-Fn wherein n is 1, Fn is the functional group, andZ* is a hydrocarbylene linking group such as an alkylene, substitutedalkylene, heteroalkylene, substituted heteroalkene, arylene, substitutedarylene, heteroarylene, or substituted heteroarylene linkage.

J is a saturated or unsaturated hydrocarbylene, substitutedhydrocarbylene, heteroatom-containing hydrocarbylene, or substitutedheteroatom-containing hydrocarbylene linkage, wherein when J issubstituted hydrocarbylene or substituted heteroatom-containinghydrocarbylene, the substituents may include one or more —(Z*)_(n)-Fngroups, wherein n is zero or 1, and Fn and Z* are as defined previously.Additionally, two or more substituents attached to ring carbon (orother) atoms within J may be linked to form a bicyclic or polycyclicolefin. J will generally contain in the range of approximately 5 to 14ring atoms, typically 5 to 8 ring atoms, for a monocyclic olefin, and,for bicyclic and polycyclic olefins, each ring will generally contain 4to 8, typically 5 to 7, ring atoms.

Mono-unsaturated cyclic olefins encompassed by structure (A) may berepresented by the structure (B)

wherein b is an integer generally although not necessarily in the rangeof 1 to 10, typically 1 to 5,

R^(A1) and R^(A2) are as defined above for structure (A), and R^(B1),R^(B2), R^(B3), R^(B4), R^(B5), and R^(B6) are independently selectedfrom the group consisting of hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl and —(Z*)_(n)-Fn where n, Z* and Fnare as defined previously, and wherein if any of the R^(B1) throughR^(B6) moieties is substituted hydrocarbyl or substitutedheteroatom-containing hydrocarbyl, the substituents may include one ormore —(Z*)_(n)-Fn groups. Accordingly, R^(B1), R^(B2), R^(B3), R^(B4),R^(B5), and R^(B6) may be, for example, hydrogen, hydroxyl, C₁-C₂₀alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl, amino, amido, nitro, etc.

Furthermore, any of the R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), andR^(B6) moieties can be linked to any of the other R^(B1), R^(B2),R^(B3), R^(B4) _(, R) ^(B5), and R^(B6) moieties to provide asubstituted or unsubstituted alicyclic group containing 4 to 30 ringcarbon atoms or a substituted or unsubstituted aryl group containing 6to 18 ring carbon atoms or combinations thereof and the linkage mayinclude heteroatoms or functional groups, e.g. the linkage may includewithout limitation an ether, ester, thioether, amino, alkylamino, imino,or anhydride moiety. The alicyclic group can be monocyclic, bicyclic, orpolycyclic. When unsaturated the cyclic group can containmonounsaturation or multiunsaturation, with monounsaturated cyclicgroups being preferred. When substituted, the rings containmonosubstitution or multisubstitution wherein the substituents areindependently selected from hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z*and Fn are as defined previously, and functional groups (Fn) providedabove.

Examples of monounsaturated, monocyclic olefins encompassed by structure(B) include, without limitation, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene,cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, andcycloeicosene, and substituted versions thereof such as1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene,1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene,4-methoxy-cyclopentene, 4-ethoxy-cyclopentene, cyclopent-3-ene-thiol,cyclopent-3-ene, 4-methylsulfanyl-cyclopentene, 3-methylcyclohexene,1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.

Monocyclic diene reactants encompassed by structure (A) may be generallyrepresented by the structure (C)

wherein c and d are independently integers in the range of 1 to about 8,typically 2 to 4, preferably 2 (such that the reactant is acyclooctadiene), R^(A1) and R^(A2) are as defined above for structure(A), and R^(C1), R^(C2), R^(C3), R^(C4), R^(C5), and R^(C6) are definedas for R^(B1) through R^(B6). In this case, it is preferred that R^(C3)and R^(C4) be non-hydrogen substituents, in which case the secondolefinic moiety is tetrasubstituted. Examples of monocyclic dienereactants include, without limitation, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene,1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene,1,3-cyclooctadiene, and substituted analogs thereof. Triene reactantsare analogous to the diene structure (C), and will generally contain atleast one methylene linkage between any two olefinic segments. Bicyclicand polycyclic olefins encompassed by structure (A) may be generallyrepresented by the structure (D)

wherein R^(A1) and R^(A2) are as defined above for structure (A),R^(D1), R^(D2), R^(D3), and R^(D4) are as defined for R^(B1) throughR^(B6), e is an integer in the range of 1 to 8 (typically 2 to 4) f isgenerally 1 or 2; T is lower alkylene or alkenylene (generallysubstituted or unsubstituted methyl or ethyl), CHR^(G1), C(R^(G1))₂, O,S, N—R^(G1), P—R^(G1), O═P—R^(G1), Si(R^(G1))₂, B—R^(G1), or As—R^(G1)where R^(G1) is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl,aralkyl, or alkoxy. Furthermore, any of the R^(D1), R^(D2), R^(D3), andR^(D4) moieties can be linked to any of the other R^(D1), R^(D2),R^(D3), and R^(D4) moieties to provide a substituted or unsubstitutedalicyclic group containing 4 to 30 ring carbon atoms or a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms orcombinations thereof and the linkage may include heteroatoms orfunctional groups, e.g. the linkage may include without limitation anether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.The cyclic group can be monocyclic, bicyclic, or polycyclic. Whenunsaturated the cyclic group can contain mono-unsaturation ormulti-unsaturation, with mono-unsaturated cyclic groups being preferred.When substituted, the rings contain mono-substitution ormulti-substitution wherein the substituents are independently selectedfrom hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z* and Fn are as definedpreviously, and functional groups (Fn) provided above.

Cyclic olefins encompassed by structure (D) are in the norbornenefamily. As used herein, norbornene means any compound that includes atleast one norbornene or substituted norbornene moiety, including withoutlimitation norbornene, substituted norbornene(s), norbornadiene,substituted norbornadiene(s), polycyclic norbornenes, and substitutedpolycyclic norbornene(s). Norbornenes within this group may be generallyrepresented by the structure (E)

wherein R^(A1) and R^(A2) are as defined above for structure (A), T isas defined above for structure (D), R^(E1), R^(E2), R^(E3), R^(E4),R^(E5), R^(E6), R^(E7) and R^(E8) are as defined for R^(B1) throughR^(B6), and “a” represents a single bond or a double bond, f isgenerally 1 or 2, “g” is an integer from 0 to 5, and when “a” is adouble bond one of R^(E5), R^(E6) and one of R^(E7), R^(E8) is notpresent. Furthermore, any of the R^(E5), R^(E6), R^(E7), and R^(E8)moieties can be linked to any of the other R^(E5), R^(E6), R^(E7), andR^(E8) moieties to provide a substituted or unsubstituted alicyclicgroup containing 4 to 30 ring carbon atoms or a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms orcombinations thereof and the linkage may include heteroatoms orfunctional groups, e.g. the linkage may include without limitation anether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.The cyclic group can be monocyclic, bicyclic, or polycyclic. Whenunsaturated the cyclic group can contain monounsaturation ormultiunsaturation, with monounsaturated cyclic groups being preferred.When substituted, the rings contain monosubstitution ormultisubstitution wherein the substituents are independently selectedfrom hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z* and Fn are as definedpreviously, and functional groups (Fn) provided above.

More preferred cyclic olefins possessing at least one norbornene moietyhave the structure (F):

wherein, R^(F1), R^(F2), R^(F3), and R^(F4), are as defined for R^(B1)through R^(B6), and “a” represents a single bond or a double bond, “g”is an integer from 0 to 5, and when “a” is a double bond one of R^(F1),R^(F2) and one of R^(F3), R^(F4) is not present.

Furthermore, any of the R^(F1), R^(F2), R^(F3), and R^(F4) moieties canbe linked to any of the other R^(F1), R^(F2), R^(F3), and R^(F4)moieties to provide a substituted or unsubstituted alicyclic groupcontaining 4 to 30 ring carbon atoms or a substituted or unsubstitutedaryl group containing 6 to 18 ring carbon atoms or combinations thereofand the linkage may include heteroatoms or functional groups, e.g. thelinkage may include without limitation an ether, ester, thioether,amino, alkylamino, imino, or anhydride moiety. The alicyclic group canbe monocyclic, bicyclic, or polycyclic. When unsaturated the cyclicgroup can contain monounsaturation or multiunsaturation, withmonounsaturated cyclic groups being preferred. When substituted, therings contain monosubstitution or multisubstitution wherein thesubstituents are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z*and Fn are as defined previously, and functional groups (Fn) providedabove.

One route for the preparation of hydrocarbyl substituted andfunctionally substituted norbornenes employs the Diels-Aldercycloaddition reaction in which cyclopentadiene or substitutedcyclopentadiene is reacted with a suitable dienophile at elevatedtemperatures to form the substituted norbornene adduct generally shownby the following reaction Scheme 4:

wherein R^(F1) to R^(F4) are as previously defined for structure (F).

Other norbornene adducts can be prepared by the thermal pyrolysis ofdicyclopentadiene in the presence of a suitable dienophile. The reactionproceeds by the initial pyrolysis of dicyclopentadiene tocyclopentadiene followed by the Diels-Alder cycloaddition ofcyclopentadiene and the dienophile to give the adduct shown below inScheme 5:

wherein “g” is an integer from 0 to 5, and R^(F1) to R^(F4) are aspreviously defined for structure (F).

Norbornadiene and higher Diels-Alder adducts thereof similarly can beprepared by the thermal reaction of cyclopentadiene anddicyclopentadiene in the presence of an acetylenic reactant as shownbelow in Scheme 6:

herein “g” is an integer from 0 to 5, R^(F1) and R^(F4) are aspreviously defined for structure (F) Examples of bicyclic and polycyclicolefins thus include, without limitation, dicyclopentadiene (DCPD);trimer and other higher order oligomers of cyclopentadiene includingwithout limitation tricyclopentadiene (cyclopentadiene trimer),cyclopentadiene tetramer, and cyclopentadiene pentamer;ethylidenenorbornene; dicyclohexadiene; norbornene;5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene;5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene;5-acetylnorbornene; 5-methoxycarbonylnorbornene;5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene;5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene;cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene;endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene;norbornadiene; tricycloundecene; tetracyclododecene;8-methyltetracyclododecene; 8-ethyltetracyclododecene;8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene;8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene;and the like, and their structural isomers, stereoisomers, and mixturesthereof. Additional examples of bicyclic and polycyclic olefins include,without limitation, C₂-C₁₂ hydrocarbyl substituted norbornenes such as5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene,5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene,5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene,5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, and the like.

Preferred cyclic olefins include C₅ to C₂₄ unsaturated hydrocarbons.Also preferred are C₅ to C₂₄ cyclic hydrocarbons that contain one ormore (typically 2 to 12) heteroatoms such as O, N, S, or P. For example,crown ether cyclic olefins may include numerous 0 heteroatoms throughoutthe cycle, and these are within the scope of the invention. In addition,preferred cyclic olefins are C₅ to C₂₄ hydrocarbons that contain one ormore (typically 2 or 3) olefins. For example, the cyclic olefin may bemono-, di-, or tri-unsaturated. Examples of cyclic olefins includewithout limitation cyclooctene, cyclododecene, and(c,t,t)-1,5,9-cyclododecatriene.

The cyclic olefins may also comprise multiple (typically 2 or 3) rings.For example, the cyclic olefin may be mono-, di-, or tri-cyclic. Whenthe cyclic olefin comprises more than one ring, the rings may or may notbe fused. Preferred examples of cyclic olefins that comprise multiplerings include norbornene, dicyclopentadiene, tricyclopentadiene, and5-ethylidene-2-norbornene.

The cyclic olefin may also be substituted, for example, a C₅ to C₂₄cyclic hydrocarbon wherein one or more (typically 2, 3, 4, or 5) of thehydrogens are replaced with non-hydrogen substituents. Suitablenon-hydrogen substituents may be chosen from the substituents describedhereinabove. For example, functionalized cyclic olefins, i.e., C₅ to C₂₄cyclic hydrocarbons wherein one or more (typically 2, 3, 4, or 5) of thehydrogens are replaced with functional groups, are within the scope ofthe invention. Suitable functional groups may be chosen from thefunctional groups described hereinabove. For example, a cyclic olefinfunctionalized with an alcohol group may be used to prepare a telechelicpolymer comprising pendent alcohol groups. Functional groups on thecyclic olefin may be protected in cases where the functional groupinterferes with the metathesis catalyst, and any of the protectinggroups commonly used in the art may be employed. Acceptable protectinggroups may be found, for example, in Greene et al., Protective Groups inOrganic Synthesis, 3rd Ed. (N.Y.: Wiley, 1999). Examples offunctionalized cyclic olefins include without limitation2-hydroxymethyl-5-norbornene,2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cydecanol,5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.

Cyclic olefins incorporating any combination of the abovementionedfeatures (i.e., heteroatoms, substituents, multiple olefins, multiplerings) are suitable for the methods disclosed herein. Additionally,cyclic olefins incorporating any combination of the abovementionedfeatures (i.e., heteroatoms, substituents, multiple olefins, multiplerings) are suitable for the invention disclosed herein.

The cyclic olefins useful in the methods disclosed herein may bestrained or unstrained. It will be appreciated that the amount of ringstrain varies for each cyclic olefin compound, and depends upon a numberof factors including the size of the ring, the presence and identity ofsubstituents, and the presence of multiple rings. Ring strain is onefactor in determining the reactivity of a molecule towards ring-openingolefin metathesis reactions. Highly strained cyclic olefins, such ascertain bicyclic compounds, readily undergo ring opening reactions witholefin metathesis catalysts. Less strained cyclic olefins, such ascertain unsubstituted hydrocarbon monocyclic olefins, are generally lessreactive. In some cases, ring opening reactions of relatively unstrained(and therefore relatively unreactive) cyclic olefins may become possiblewhen performed in the presence of the olefinic compounds disclosedherein. Additionally, cyclic olefins useful in the invention disclosedherein may be strained or unstrained.

A plurality of cyclic olefins may be used with the present invention toprepare metathesis polymers. For example, two cyclic olefins selectedfrom the cyclic olefins described hereinabove may be employed in orderto form metathesis products that incorporate both cyclic olefins. Wheretwo or more cyclic olefins are used, one example of a second cyclicolefin is a cyclic alkenol, i.e., a C₅-C₂₄ cyclic hydrocarbon wherein atleast one of the hydrogen substituents is replaced with an alcohol orprotected alcohol moiety to yield a functionalized cyclic olefin.

The use of a plurality of cyclic olefins, and in particular when atleast one of the cyclic olefins is functionalized, allows for furthercontrol over the positioning of functional groups within the products.For example, the density of cross-linking points can be controlled inpolymers and macromonomers prepared using the methods disclosed herein.Control over the quantity and density of substituents and functionalgroups also allows for control over the physical properties (e.g.,melting point, tensile strength, glass transition temperature, etc.) ofthe products. Control over these and other properties is possible forreactions using only a single cyclic olefin, but it will be appreciatedthat the use of a plurality of cyclic olefins further enhances the rangeof possible metathesis products and polymers formed.

More preferred cyclic olefins include dicyclopentadiene;tricyclopentadiene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene;5-ethyl-2-norbornene; 5-isobutyl-2-norbornene;5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene;5-acetylnorbornene; 5-methoxycarbonylnorbornene;5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene;5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene;cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo, exo-5-6-dimethoxycarbonylnorbornene;endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene;norbornadiene; tricycloundecene; tetracyclododecene;8-methyltetracyclododecene; 8-ethyl-tetracyclododecene;8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclo-dodecene;8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene;higher order oligomers of cyclopentadiene such as cyclopentadienetetramer, cyclopentadiene pentamer, and the like; and C₂-C₁₂ hydrocarbylsubstituted norbornenes such as 5-butyl-2-norbornene;5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene;5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene;5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; and5-butenyl-2-norbornene, and the like. Even more preferred cyclic olefinsinclude dicyclopentadiene, tricyclopentadiene, and higher orderoligomers of cyclopentadiene, such as cyclopentadiene tetramer,cyclopentadiene pentamer, and the like, tetracyclododecene, norbornene,and C₂-C₁₂ hydrocarbyl substituted norbornenes, such as5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene,5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene,5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene,5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.

Tethered Polymer Arrays

To this point, the methods have been described in terms of growingproduct polymer(s), without regard for orientation or attachment of theresulting polymers. While various embodiments do provide that themethods may be used to form loose, unattached, or “free-standing”polymers, the methods also may be used to grow polymers which aretethered or attached to a substrate surface, either through singlepoints or attachment at one end, or through multiple “engagement points”along the length of the polymer; i.e., where the polymer is bound to asubstrate surface. In either case, the resulting polymers may beattached to the substrate surface by covalent bonding, hydrogen bonding,ionic bonding, physisorption, pi-pi interaction, Van der Waals forces,or a combination thereof. These points of attachments may be vialinkages comprising functional groups such as amino, carbene,carboxylate, catecholate, a dithiocarbamate, dithioic acid, hydroxy,hydroxyamic acid, isocyanato, nitrite, phosphate, phosphonate, a silaneor silicate, or thiol groups. One of ordinary skill in the art would befamiliar with these and other chemical groups that are able to form anattachment to the surface.

In describing such polymers which are tethered or attached to asubstrate surface at one end, it is useful to describe an individualpolymer as having proximal and distal ends, in which the proximal end(s)is/are those ends closest or tethered to the surface, and the distalend(s) is/are those ends of the polymers which stand away from thesubstrate surface. While not intending to be bound by the correctness orincorrectness of any particular theory, it may be useful to view thegrowth of such a polymer, tethered at its proximal end to the substratesurface, as resulting from a metathesis reaction in which the metathesiscatalyst remains bonded to and reacts with gaseous or vapor precursor atthe “living,” distal end of the polymer, for example by a carbenelinkage. As the methods proceed, the polymer product grows, eitherindividually or as a plurality of individual polymer strands via theassociated metathesis reactions, so as to extend away from the surface.

Such a tethered structure may be formed, for example, by pre-reacting asecond, end-functionalized olefinic or acetylenic precursor with asurface, under conditions sufficient to attach the end-functionalizedolefinic or acetylenic precursor to the surface. The term “second,end-functionalized” is intended to connote that this precursor may bethe same or different from the feedstock precursor used in themetathesis reaction(s), in terms of the nature of the unsaturatedmoiety, and that it contains a functional group (as described above)useful for bonding to the substrate. Once in place, for example as amonolayer on the substrate, the second, end-functionalized precursor ismodified to incorporate the catalyst complex. This may be accomplishedby reacting the second, end-functionalized precursor, now tethered, witha suitable metathesis catalyst, with or without solvent, to form thenecessary initiator for the subsequent metathesis reaction(s). Note thatif solvent is used during the generation of this initiator, it is to beremoved—by vacuum, heat, or both—prior to operating the inventivemethods. Once the metathesis catalyst is tethered to the surface, viathe second, end-functionalized precursor, the feedstock is introduced toinitiate the polymerization of a linear chain with the catalyst at theterminus The growing polymer chain terminates at a double bonded betweena carbon and a metal center of the catalyst. Accordingly, the catalystremains at the terminal, distal end of the growing polymer chain and thegrowth occurs by adding additional feedstock precursors to the terminal,distal end of the polymer chain.

These concepts are illustrated in FIG. 1.

Another way of generating this initiator monolayer is to use ametathesis catalyst, which already contains the functional groupnecessary for attachment to the surface. In such embodiments, thecatalyst may be deposited from a solution, where the solution solvent isremoved before the conditions associated with the direct vapor/solidphase or direct gas/solid phase polymerization are employed.

The terms “surface,” “substrate” and “substrate material” as usedherein, are intended to generally mean any material from which thetethered polymers grow, or where the catalytic initiators are contactedwith, applied to, or bonded to. These terms may be viewed in terms ofplanar or substantially planar (e.g., curved or undulating) surfaces,but also include particulate (e.g., spherical or oblate) or elongatedsurfaces (e.g., cylindrically shaped tubes or fibers), having at leastone dimension in the nanometer range (e.g., in a range from about 1 nmto about 1000 nm), micron range (e.g., in a range from about 1 micron toabout 1000 micron), or larger (e.g., in a range from about 1 cm andabove), or a combination thereof.

In those embodiments where the polymer product is “grown” from asurface, the surface may comprise a synthetic, semi-synthetic, ornaturally occurring materials, which may be organic or inorganic, e.g.,polymeric, ceramic, or metallic. Without limitation, such materialsinclude metals, metal oxides, polymers, glass, ceramics, filaments,fibers, rovings, mats, weaves, fabrics, knitted material, cloth or otherknown structures, glass fibers and fabrics, carbon fibers and fabrics,aramid fibers and fabrics, polyolefin or other polymer fibers orfabrics, any material possessing a surface containing hydroxylfunctional groups, silicas, silicates, aluminas, aluminum oxides,silica-aluminas, aluminosilicates, zeolites, titanias, titanium dioxide,magnetite, magnesium oxides, boron oxides, clays, zirconias, zirconiumdioxide, carbon, titanium oxides, silicon oxides, iron oxides, indiumtin oxide (ITO), fluorine tin oxide (PTO), gallium arsenide oxides,copper oxides, zirconium oxides, zinc oxides, yttrium oxides, cellulose,cellulosic polymers amylose, amylosic polymers, or a combinationthereof. Preferred exemplary, non-limiting surfaces include thosecomprising Au, Ag, Cu, Pd, Pt, GaAs, oxides of Al, Cu, Fe, Si, Ti, Y,Zn, Zr, or mixed oxides such as silicate glasses, indium-tin-oxide(ITO), or fluorine tin oxide (FTO).

It should be apparent that the combination of substrates and potentialpolymer compositions described herein can yield any combination ofconducting/semiconducting surface and conducting/semiconducting polymer.Where appropriate, it is preferred that the tethering moiety is eithernon-insulative or can allow electron hopping. It should also be apparentthat the initiator moieties may be patterned on the relevant surface,for example, by use of photomasking technology, by selective depositionof the catalyst, or both.

One of the many attractive features of the methods described herein isthe ability of these methods to provide patterned arrays of orientedpolymer strands or arrays. The active or final polymer chains may bealigned with one another or, depending on the length of the polymerstrands, may form disarrayed mats. When aligned, each active polymerextends away from the surface. In certain embodiments, the individualpolymer strands may be described as substantially parallel to oneanother. Assuming the polymer chains are substantially linear, thismeasure of alignment can be described in terms imaginary end-to-endvector which can be envisioned to extend between the proximal and distalends of the individual polymer chains. Alignment is achieved when theselines are parallel or substantially parallel to one another. Forinstance, each line can have an angle relative to the surface (θ_(x)),and the average of the individual lines can be used to define an averageangle between each line and the first surface (θ,_(avg)). The alignmentof the polymers can be described, using these terms, by the portion ofthe individual polymers (e.g., more than 50%, 75%, or even 90%) whoseangle relative to the surface (θ_(x)) that is within some measure (e.g.,+/−40°, 20°, 10°, or 5°) of the angle (θ,_(avg)). Additionally oralternately, the angle (θ,_(avg)) itself can be used to describe theorientation of the polymer array with respect to the surface. The term“substantially parallel” refers to a condition where the angles of theindividual polymer strands are collectively ±20° of angle, θ,_(avg). Inother embodiments, the polymer arrays are normal to the surface of thesubstrate, where normal is defined as when θ,_(avg) is within ±20° of90°. The methods described in this disclosure are especially usefulbecause the 2-dimensional confinement of the catalysts enables thealignment of polymers to these levels. This is especially attractive forthose polymers having properties useful for optical or electronicdevices, when tethered to one or more electrode surfaces.

The use of self-assembled monolayers allows the first anchoring groupsto be densely packed on the optionally patterned surface. Growing thepolymer chains on densely packed first anchoring groups keeps thepolymer chains densely packed. Additionally, the consistency in the rateat which each chain grows effectively causes the polymer chains to beformed one layer at a time. The combination of the dense packing andforming the polymer chains in layers causes the pattern in which thefirst anchoring groups 16 are arranged on the surface to be retainedthrough the polymer chains as discussed above.

Performing direct gas/solid phase polymerization reactions may provideeven further alignment of the polymer chains. For instance, the rate ofdiffusion of the catalyst in is significantly lower at a vapor/solidinterface (even where localized condensation of the feedstock precursorresult in a localized liquid/solid interface) than in solution.Diffusion is even lower at a direct gas/solid phase interface (wheresuch localized condensation of the feedstock precursor is much lesslikely, if not impossible). This reduced rate of diffusion reduces theopportunity for the polymer chains to change directions during growth.As a result, performing the ring-opening metathesis polymerizationsusing a direct gas/solid phase interface can further enhance of thealignment of the polymer chains.

Transition Metal-Based Metathesis Catalysts

Transition metal-based metathesis catalysts suitable for use in alkeneor alkyne metathesis chemistry include those alkylidene or alkylidynecomplexes (or precursors which may generated organometallic alkylideneor alkylidyne complexes) comprising Mo, Pd, Ru, Ta, Ti, or W.Non-limiting examples include systems based on structures such as:

While such catalyst systems are known in solvent based metathesescontexts, to the inventors' knowledge, none of these have been appliedto direct vapor solid phase or direct gas/solid phase reactions, nor arethey known to be useful in this context. Yet these, and derivativesthereof, may be suitable for use in the reactions described herein.

Organometallic complexes based on Group 8 metals, especially osmium andruthenium, especially those of ruthenium containing N-heterocycliccarbene ligands, are especially useful in the embodiments describedherein. In particular, the various generations of complexes known asGrubbs' catalyst, are preferred. These catalysts have been described,inter alia, in U.S. Pat. Nos. 5,312,940; 5,342,909; 5,750,815;5,831,108; 5,917,071; 5,969,170; 5,977,393; 6,048,993; 6,111,121;6,153,778; 6,211,391; 6,284,852; 6,313,332; 6,426,419; 6,486,279;6,504,041; 6,515,084; 6,624,265; 6,759,537; 6,806,325; 6,818,586;7,102,047; 7,288,666; 7,329,758; and 7,750,172 and U.S. PatentApplication Publ. Nos. 2001/0039360; 2002/0013473; 2002/0022733;2002/0055598; 2002/0177710; 2003/0069374; 2003/0181609; 2005/0113590;2006/0241317; 2009/0012248; 2009/0012254; and 2011/0124868, each ofwhich is incorporated by reference for its teaching of catalyst andcatalyst precursor structure. The term “Grubbs-type catalyst” isintended to embrace one or more of the structures described below(including First and Second Generation Grubbs-Type catalysts andGrubbs-Hoveyda catalysts), and the term “Grubbs-type rutheniumcatalysts” likewise connotes those Grubbs-type catalyst structures whereM is Ru.

In certain embodiments of the present invention, the transitionmetal-based metathesis catalyst complex is preferably a Group 8transition metal complex having the structure of formula (I)

in which:

M is a Group 8 transition metal;

L¹, L², and L³ are neutral electron donor ligands;

n is 0 or 1, such that L³ may or may not be present;

m is 0, 1, or 2;

k is 0 or 1;

X¹ and X² are anionic ligands; and

R¹ and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups,

wherein any two or more of X¹, X², L¹, L², L³, R¹, and R² can be takentogether to form one or more cyclic groups.

Additionally, in formula (I), one or both of R¹ and R² may have thestructure —(W)_(n)—U⁺V⁻, in which W is selected from hydrocarbylene,substituted hydrocarbylene, heteroatom-containing hydrocarbylene, orsubstituted heteroatom-containing hydrocarbylene; U is a positivelycharged Group 15 or Group 16 element substituted with hydrogen,hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,or substituted heteroatom-containing hydrocarbyl; V is a negativelycharged counterion; and n is zero or 1. Furthermore, R¹ and R² may betaken together to form an indenylidene moiety.

Preferred catalysts contain Ru or Os as the Group 8 transition metal,with Ru particularly preferred.

Numerous embodiments of the catalysts useful in the reactions disclosedherein are described in more detail infra. For the sake of convenience,the catalysts are described in groups, but it should be emphasized thatthese groups are not meant to be limiting in any way. That is, any ofthe catalysts useful in the invention may fit the description of morethan one of the groups described herein.

A first group of catalysts, then, are commonly referred to as FirstGeneration Grubbs-type catalysts, and have the structure of formula (I).For the first group of catalysts, M is a Group 8 transition metal, m is0, 1, or 2, and n, X¹, X², L¹, L², L³, R¹, and R² are described asfollows. For the first group of catalysts, n is 0, and L¹ and L² areindependently selected from phosphine, sulfonated phosphine, phosphite,phosphinite, phosphonite, arsine, stibine, ether, (including cyclicethers), amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine,substituted pyridine, imidazole, substituted imidazole, pyrazine,substituted pyrazine and thioether. Exemplary ligands are trisubstitutedphosphines. Preferred trisubstituted phosphines are of the formulaPR^(H1)R^(H2)R^(H3), where R^(H1), R^(H2), and R^(H3) are eachindependently substituted or unsubstituted aryl or C₁-C₁₀ alkyl,particularly primary alkyl, secondary alkyl, or cycloalkyl. In the mostpreferred, L¹ and L² are independently selected from the groupconsisting of trimethylphosphine (PMe₃), triethylphosphine (PEt₃),tri-n-butylphosphine (PBu₃), tri(ortho-tolyl)phosphine (P-o-tolyl₃),tri-tert-butylphosphine (P-tert-Bu₃), tricyclopentylphosphine(PCyclopentyl₃), tricyclohexylphosphine (PCy₃), triisopropylphosphine(P-i-Pr₃), trioctylphosphine (POct₃), triisobutylphosphine, (P-i-Bu₃),triphenylphosphine (PPh₃), tri(pentafluorophenyl)phosphine (P(C₆F₅)₃),methyldiphenylphosphine (PMePh₂), dimethylphenylphosphine (PMe₂Ph), anddiethylphenylphosphine (PEt₂Ph). Alternatively, L¹ and L² may beindependently selected from phosphabicycloalkane (e.g. monosubstituted9-phosphabicyclo-[3.3.1]nonane, or monosubstituted9-phosphabicyclo[4.2.1]nonane] such as cyclohexylphoban,isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphobanand the like).

X¹ and X² are anionic ligands, and may be the same or different, or arelinked together to form a cyclic group, typically although notnecessarily a five- to eight-membered ring. In preferred embodiments, X¹and X² are each independently hydrogen, halide, or one of the followinggroups: C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀alkoxycarbonyl, C₆-C₂₄ aryloxycarbonyl, C₂-C₂₄ acyl, C₂-C₂₄ acyloxy,C₁-C₂₀ alkylsulfonato, C₅-C₂₄ arylsulfonato, C₁-C₂₀ alkylsulfanyl,C₅-C₂₄ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, NO₃, —N═C═O, —N═C═S, orC₅-C₂₄ arylsulfinyl. Optionally, X¹ and X² may be substituted with oneor more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₂₄ aryl,and halide, which may, in turn, with the exception of halide, be furthersubstituted with one or more groups selected from halide, C₁-C₆ alkyl,C₁-C₆ alkoxy, and phenyl. In more preferred embodiments, X¹ and X² arehalide, benzoate, C₂-C₆ acyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkyl,phenoxy, C₁-C₆ alkoxy, C₁-C₆ alkylsulfanyl, aryl, or C₁-C₆alkylsulfonyl. In even more preferred embodiments, X¹ and X² are eachhalide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO,PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. In themost preferred embodiments, X¹ and X² are each chloride.

R¹ and R² are independently selected from hydrogen, hydrocarbyl (e.g.,C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), substituted hydrocarbyl (e.g.,substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl,C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), heteroatom-containing hydrocarbyl(e.g., heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), andsubstituted heteroatom-containing hydrocarbyl (e.g., substitutedheteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl,C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and functionalgroups. R¹ and R² may also be linked to form a cyclic group, which maybe aliphatic or aromatic, and may contain substituents, heteroatoms, orboth. Generally, such a cyclic group will contain 4 to 12, preferably 5,6, 7, or 8 ring atoms. In preferred catalysts, R¹ is hydrogen and R² isselected from C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₅-C₂₄ aryl, morepreferably C₁-C₆ alkyl, C₂-C₆ alkenyl, and C₅-C₁₄ aryl. Still morepreferably, R² is phenyl, vinyl, methyl, isopropyl, or t-butyl,optionally substituted with one or more moieties selected from C₁-C₆alkyl, C₁-C₆ alkoxy, phenyl, and a functional group Fn as definedearlier herein. Most preferably, R² is phenyl or vinyl substituted withone or more moieties selected from methyl, ethyl, chloro, bromo, iodo,fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. Optimally, R²is phenyl or —CH═C(CH₃)₂.

Any two or more (typically two, three, or four) of X¹, X², L¹, L², L³,R¹, and R² can be taken together to form a cyclic group, includingbidentate or multidentate ligands, as disclosed, for example, in U.S.Pat. No. 5,312,940, the disclosure of which is incorporated herein byreference. When any of X¹, X², L¹, L², L³, R¹, and R² are linked to formcyclic groups, those cyclic groups may contain 4 to 12, preferably 4, 5,6, 7 or 8 atoms, or may comprise two or three of such rings, which maybe either fused or linked. The cyclic groups may be aliphatic oraromatic, and may be heteroatom-containing or substituted. The cyclicgroup may, in some cases, form a bidentate ligand or a tridentateligand. Examples of bidentate ligands include, but are not limited to,bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.

A second group of catalysts, commonly referred to as Second GenerationGrubbs-type catalysts, have the structure of formula (I), wherein L¹ isa carbene ligand having the structure of formula (II)

such that the complex may have the structure of formula (III)

wherein M, m, n, X¹, X², L², L³, R¹, and R² are as defined for the firstgroup of catalysts, and the remaining substituents are as follows;

X and Y are heteroatoms typically selected from N, O, S, and P. Since Oand S are divalent, p is necessarily zero when X is O or S, q isnecessarily zero when Y is O or S, and k is zero or 1. However, when Xis N or P, then p is 1, and when Y is N or P, then q is 1. In apreferred embodiment, both X and Y are N;

Q¹, Q², Q³, and Q⁴ are linkers, e.g., hydrocarbylene (includingsubstituted hydrocarbylene, heteroatom-containing hydrocarbylene, andsubstituted heteroatom-containing hydrocarbylene, such as substituted,heteroatom-containing alkylene, or both) or —(CO)—, and w, x, y, and zare independently zero or 1, meaning that each linker is optional.Preferably, w, x, y, and z are all zero. Further, two or moresubstituents on adjacent atoms within Q¹, Q², Q³, and Q⁴ may be linkedto form an additional cyclic group; and

R³, R^(3A), R⁴, and R^(4A) are independently selected from hydrogen,hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,and substituted heteroatom-containing hydrocarbyl. In addition, X and Ymay be independently selected from carbon and one of the heteroatomsmentioned above. Also, L² and L³ may be taken together to form a singlebindentate electron-donating heterocyclic ligand. Furthermore, R¹ and R²may be taken together to form an indenylidene moiety. Moreover, X¹, X²,L², L³, X and Y may be further coordinated to boron or to a carboxylate.

In addition, any two or more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A),R⁴, R^(4A), Q¹, Q², Q³, and Q⁴ can be taken together to form a cyclicgroup. Any two or more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A), R⁴,and R^(4A) can also be taken to be -A-Fn, wherein “A” is a divalenthydrocarbon moiety selected from alkylene and arylalkylene, wherein thealkyl portion of the alkylene and arylalkylene groups can be linear orbranched, saturated or unsaturated, cyclic or acyclic, and substitutedor unsubstituted, wherein the aryl portion of the of arylalkylene can besubstituted or unsubstituted, and wherein hetero atoms and functionalgroups may be present in either the aryl or the alkyl portions of thealkylene and arylalkylene groups, and Fn is a functional group, ortogether to form a cyclic group.

Preferably, R^(3A) and R^(4A) are linked to form a cyclic group so thatthe carbene ligand has the structure of formula (IV)

wherein R³ and R⁴ are as defined for the second group of catalystsabove, with preferably at least one of R³ and R⁴, and more preferablyboth R³ and R⁴, being alicyclic or aromatic of one to about five rings,and optionally containing one or more heteroatoms, or substituents, orboth. Q is a linker, typically a hydrocarbylene linker, includingsubstituted hydrocarbylene, heteroatom-containing hydrocarbylene, andsubstituted heteroatom-containing hydrocarbylene linkers, wherein two ormore substituents on adjacent atoms within Q may also be linked to forman additional cyclic structure, which may be similarly substituted toprovide a fused polycyclic structure of two to about five cyclic groups.Q is often, although not necessarily, a two-atom linkage or a three-atomlinkage.

Examples of N-heterocyclic carbene (NHC) ligands and acyclicdiaminocarbene ligands suitable as L¹ thus include, but are not limitedto, the following where DIPP or DiPP is diisopropylphenyl and Mes is2,4,6-trimethylphenyl:

Additional examples of N-heterocyclic carbene (NHC) ligands and acyclicdiaminocarbene ligands suitable as L¹ thus include, but are not limitedto the following:

wherein R^(W1), R^(W2), R^(W3), R^(W4) are independently hydrogen,unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatomcontaining hydrocarbyl, and where one or both of R^(W3) and R^(W4) maybe in independently selected from halogen, nitro, amido, carboxyl,alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups.

Additional examples of N-heterocyclic carbene (NHC) ligands suitable asL¹ are further described in U.S. Pat. Nos. 7,378,528; 7,652,145;7,294,717; 6,787,620; 6,635,768; and 6,552,139 the contents of each areincorporated herein by reference.

When M is ruthenium, then, the preferred complexes have the structure offormula (V)

In a more preferred embodiment, Q is a two-atom linkage having thestructure —CR¹¹R¹²—CR¹³R¹⁴— or —CR¹¹═CR¹³—, preferably —CR¹¹R¹²—CR¹³R¹⁴,wherein R¹¹, R¹², R¹³, and R¹⁴ are independently selected from hydrogen,hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,substituted heteroatom-containing hydrocarbyl, and functional groups.Examples of functional groups here include without limitation carboxyl,C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₄alkoxycarbonyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylthio, C₅-C₂₄ arylthio,C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀ alkylsulfinyl, optionally substitutedwith one or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy,C₅-C₁₄ aryl, hydroxyl, sulfhydryl, formyl, and halide. R¹¹, R¹², R¹³,and R¹⁴ are preferably independently selected from hydrogen, C₁-C₁₂alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two ofR¹¹, R¹², R¹³, and R¹⁴ may be linked together to form a substituted orunsubstituted, saturated or unsaturated ring structure, e.g., a C₄-C₁₂alicyclic group or a C₅ or C₆ aryl group, which may itself besubstituted, e.g., with linked or fused alicyclic or aromatic groups, orwith other substituents. In one further aspect, any one or more of R¹¹,R¹², R¹³, and R¹⁴ comprises one or more of the linkers. Additionally, R³and R⁴ may be unsubstituted phenyl or phenyl substituted with one ormore substituents selected from C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl,C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl,substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl, C₆-C₂₄ aralkyl, C₆-C₂₄alkaryl, or halide. Furthermore, X¹ and X² may be halogen.

When R³ and R⁴ are aromatic, they are typically although not necessarilycomposed of one or two aromatic rings, which may or may not besubstituted, e.g., R³ and R⁴ may be phenyl, substituted phenyl,biphenyl, substituted biphenyl, or the like. In one preferredembodiment, R³ and R⁴ are the same and are each unsubstituted phenyl orphenyl substituted with up to three substituents selected from C₁-C₂₀alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl,C₆-C₂₄ aralkyl, C₆-C₂₄ alkaryl, or halide. Preferably, any substituentspresent are hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl,substituted C₅-C₁₄ aryl, or halide. As an example, R³ and R⁴ are mesityl(i.e. Mes as defined herein).

In a third group of catalysts having the structure of formula (I), M, m,n, X¹, X², R¹, and R² are as defined for the first group of catalysts,L¹ is a strongly coordinating neutral electron donor ligand such as anyof those described for the first and second group of catalysts, and L²and L³ are weakly coordinating neutral electron donor ligands in theform of optionally substituted heterocyclic groups. Again, n is zero or1, such that L³ may or may not be present. Generally, in the third groupof catalysts, L² and L³ are optionally substituted five- or six-memberedmonocyclic groups containing 1 to 4, preferably 1 to 3, most preferably1 to 2 heteroatoms, or are optionally substituted bicyclic or polycyclicstructures composed of 2 to 5 such five- or six-membered monocyclicgroups. If the heterocyclic group is substituted, it should not besubstituted on a coordinating heteroatom, and any one cyclic moietywithin a heterocyclic group will generally not be substituted with morethan 3 substituents.

For the third group of catalysts, examples of L² and L³ include, withoutlimitation, heterocycles containing nitrogen, sulfur, oxygen, or amixture thereof.

Examples of nitrogen-containing heterocycles appropriate for L² and L³include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine,pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole,2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole,1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine,indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline,cinnoline, quinazoline, naphthyridine, piperidine, piperazine,pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine,purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole.Additionally, the nitrogen-containing heterocycles may be optionallysubstituted on a non-coordinating heteroatom with a non-hydrogensubstitutent.

Examples of sulfur-containing heterocycles appropriate for L² and L³include thiophene, 1,2-dithiole, 1,3-dithiole, thiepin,benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene,2H-thiopyran, 4H-thiopyran, and thioanthrene.

Examples of oxygen-containing heterocycles appropriate for L² and L³include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin,oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene,chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene,tetrahydrofuran, 1,4-dioxan, and dibenzofuran. Examples of mixedheterocycles appropriate for L² and L³ include isoxazole, oxazole,thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole,1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole,3H-1,2,3-dioxazole, 3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine,2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine,phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine,benzoxazole, anthranil, and morpholine.

Preferred L² and L³ ligands are aromatic nitrogen-containing andoxygen-containing heterocycles, and particularly preferred L² and L³ligands are monocyclic N-heteroaryl ligands that are optionallysubstituted with 1 to 3, preferably 1 or 2, substituents. Specificexamples of particularly preferred L² and L³ ligands are pyridine andsubstituted pyridines, such as 3-bromopyridine, 4-bromopyridine,3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine,3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine,2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine,3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine,3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine,3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine,2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine,4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine,3,5-dichloro-4-phenylpyridine, and the like.

In general, any substituents present on either or both of L²L³ areselected from halo, C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀heteroalkyl, substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substitutedC₅-C₂₄ aryl, C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, C₆-C₂₄alkaryl, substituted C₆-C₂₄ alkaryl, C₆-C₂₄ heteroalkaryl, substitutedC₆-C₂₄ heteroalkaryl, C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, C₆-C₂₄heteroaralkyl, substituted C₆-C₂₄ heteroaralkyl, and functional groups,with suitable functional groups including, without limitation, C₁-C₂₀alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkylcarbonyl, C₆-C₂₄ arylcarbonyl,C₂-C₂₀ alkylcarbonyloxy, C₆-C₂₄ arylcarbonyloxy, C₂-C₂₀ alkoxycarbonyl,C₆-C₂₄ aryloxycarbonyl, halocarbonyl, C₂-C₂₀ alkylcarbonato, C₆-C₂₄arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C₁-C₂₀alkyl)-substituted carbamoyl, di-(C₁-C₂₀ alkyl)-substituted carbamoyl,di-N—(C₁-C₂₀ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl, mono-(C₅-C₂₄aryl)-substituted carbamoyl, di-(C₆-C₂₄ aryl)-substituted carbamoyl,thiocarbamoyl, mono-(C₁-C₂₀ alkyl)-substituted thiocarbamoyl, di-(C₁-C₂₀alkyl)-substituted thiocarbamoyl, di-N—(C₁-C₂₀ alkyl)-N—(C₆-C₂₄aryl)-substituted thiocarbamoyl, mono-(C₆-C₂₄ aryl)-substitutedthiocarbamoyl, di-(C₆-C₂₄ aryl)-substituted thiocarbamoyl, carbamido,formyl, thioformyl, amino, mono-(C₁-C₂₀ alkyl)-substituted amino,di-(C₁-C₂₀ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substitutedamino, di-(C₅-C₂₄ aryl)-substituted amino, di-N—(C₁-C₂₀ alkyl),N—(C₅-C₂₄ aryl)-substituted amino, C₂-C₂₀ alkylamido, C₆-C₂₄ arylamido,imino, C₁-C₂₀ alkylimino, C₅-C₂₄ arylimino, nitro, and nitroso. Inaddition, two adjacent substituents may be taken together to form aring, generally a five- or six-membered alicyclic or aryl ring,optionally containing 1 to 3 heteroatoms and 1 to 3 substituents asabove.

Preferred substituents on L² and L³ include, without limitation, halo,C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substitutedC₁-C₁₂ heteroalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, C₅-C₁₄heteroaryl, substituted C₅-C₁₄ heteroaryl, C₆-C₁₆ alkaryl, substitutedC₆-C₁₆ alkaryl, C₆-C₁₆ heteroalkaryl, substituted C₆-C₁₆ heteroalkaryl,C₆-C₁₆ aralkyl, substituted C₆-C₁₆ aralkyl, C₆-C₁₆ heteroaralkyl,substituted C₆-C₁₆ heteroaralkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryloxy, C₂-C₁₂alkylcarbonyl, C₆-C₁₄ arylcarbonyl, C₂-C₁₂ alkylcarbonyloxy, C₆-C₁₄arylcarbonyloxy, C₂-C₁₂ alkoxycarbonyl, C₆-C₁₄ aryloxycarbonyl,halocarbonyl, formyl, amino, mono-(C₁-C₁₂ alkyl)-substituted amino,di-(C₁-C₁₂ alkyl)-substituted amino, mono-(C₅-C₁₄ aryl)-substitutedamino, di-(C₅-C₁₄ aryl)-substituted amino, and nitro.

Of the foregoing, the most preferred substituents are halo, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₁-C₆ alkoxy, phenyl, substituted phenyl, formyl,N,N-di(C₁-C₆ alkyl)amino, nitro, and nitrogen heterocycles as describedabove (including, for example, pyrrolidine, piperidine, piperazine,pyrazine, pyrimidine, pyridine, pyridazine, etc.).

In certain embodiments, L² and L³ may also be taken together to form abidentate or multidentate ligand containing two or more, generally two,coordinating heteroatoms such as N, O, S, or P, with preferred suchligands being diimine ligands of the Brookhart type. One representativebidentate ligand has the structure of formula (VI)

wherein R¹⁵, R¹⁶,R¹⁷, and R¹⁸ hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄aralkyl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄aralkyl), heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl,C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, orheteroatom-containing C₆-C₂₄ alkaryl), or substitutedheteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl,C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, orheteroatom-containing C₆-C₂₄ alkaryl), or (1) R¹⁵ and R¹⁶, (2) R¹⁷ andR¹⁸, (3) R¹⁶ and R¹⁷, or (4) both R¹⁵ and R¹⁶, and R¹⁷ and R¹⁸, may betaken together to form a ring, i.e., an N-heterocycle. Preferred cyclicgroups in such a case are five- and six-membered rings, typicallyaromatic rings.

In a fourth group of catalysts that have the structure of formula (I),two of the substituents are taken together to form a bidentate ligand ora tridentate ligand. Examples of bidentate ligands include, but are notlimited to, bisphosphines, dialkoxides, alkyldiketonates, andaryldiketonates. Specific examples include —P(Ph)₂CH₂CH₂P(Ph)₂-,—As(Ph)₂CH₂CH₂As(Ph₂)-, —P(Ph)₂CH₂CH₂C(CF₃)₂O—, binaphtholate dianions,pinacolate dianions, —P(CH₃)₂(CH₂)₂P(CH₃)₂—, and —OC(CH₃)₂(CH₃)₂CO—.Preferred bidentate ligands are —P(Ph)₂ CH₂CH₂P(Ph)₂- and—P(CH₃)₂(CH₂)₂P(CH₃)₂—. Tridentate ligands include, but are not limitedto, (CH₃)₂NCH₂CH₂P(Ph)CH₂CH₂N(CH₃)₂. Other preferred tridentate ligandsare those in which any three of X¹, X², L¹, L², L³, R¹, and R² (e.g.,X¹, L¹, and L²) are taken together to be cyclopentadienyl, indenyl, orfluorenyl, each optionally substituted with C₂-C₂₀ alkenyl, C₂-C₂₀alkynyl, C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy,C₂-C₂₀ alkynyloxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀alkylthio, C₁-C₂₀ alkylsulfonyl, or C₁-C₂₀ alkylsulfinyl, each of whichmay be further substituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy orwith a phenyl group optionally substituted with halide, C₁-C₆ alkyl, orC₁-C₆ alkoxy. More preferably, in compounds of this type, X, L¹, and L²are taken together to be cyclopentadienyl or indenyl, each optionallysubstituted with vinyl, C₁-C₁₀ alkyl, C₅-C₂₀ aryl, C₁-C₁₀ carboxylate,C₂-C₁₀ alkoxycarbonyl, C₁-C₁₀ alkoxy, or C₅-C₂₀ aryloxy, each optionallysubstituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy or with a phenylgroup optionally substituted with halide, C₁-C₆ alkyl or C₁-C₆ alkoxy.Most preferably, X, L¹ and L² may be taken together to becyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl,or phenyl. Tetradentate ligands include, but are not limited toO₂C(CH₂)₂P(Ph)(CH₂)₂P(Ph)(CH₂)₂CO₂, phthalocyanines, and porphyrins.

Complexes wherein Y is coordinated to the metal are examples of a fifthgroup of catalysts, and are commonly called “Grubbs-Hoveyda” catalysts.Grubbs-Hoveyda metathesis-active metal carbene complexes may bedescribed by the formula (VII)

wherein,

M is a Group 8 transition metal, particularly Ru or Os, or, moreparticularly, Ru;

X¹, X², and L¹ are as previously defined herein for the first and secondgroups of catalysts;

Y is a heteroatom selected from N, O, S, and P; preferably Y is O or N;

R⁵, R⁶, R⁷, and R⁸ are each, independently, selected from the groupconsisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl,heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl,alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino,alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl,alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano,isocyanate, hydroxyl, ester, ether, amine, imine, amide,halogen-substituted amide, trifluoroamide, sulfide, disulfide,sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or-A-Fn, wherein “A” and Fn have been defined above; and any combinationof Y, Z, R⁵, R⁶, R⁷, and R⁸ can be linked to form one or more cyclicgroups;

n is 0, 1, or 2, such that n is 1 for the divalent heteroatoms O or S,and n is 2 for the trivalent heteroatoms N or P; and

Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl,functionalized aryl where the functional group(s) may independently beone or more or the following: alkoxy, aryloxy, halogen, carboxylic acid,ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether,amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate,silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl,sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl.Additionally, R⁵, R⁶, R⁷, R⁸, and Z may independently be thioisocyanate,cyanato, or thiocyanato.

In general, Grubbs-Hoveyda complexes useful in the invention contain achelating alkylidene moiety of the formula (VIII)

wherein Y, n, Z, R⁵, R⁶, R⁷, and R⁸ are as previously defined herein;

Y, Z, and R⁵ can optionally be linked to form a cyclic structure; and

R⁹ and R¹⁶ are each, independently, selected from hydrogen or asubstituent group selected from alkyl, aryl, alkoxy, aryloxy, C₂-C₂₀alkoxycarbonyl, or C₁-C₂₀ trialkylsilyl, wherein each of the substituentgroups is substituted or unsubstituted. The chelating alkylidene moietymay be derived from a ligand precursor having the formula:

Non-limiting examples of complexes comprising Grubbs-Hoveyda ligandssuitable in the invention include:

wherein, L¹, X¹, X², and M are as described for any of the other groupsof catalysts. Suitable chelating carbenes and carbene precursors arefurther described by Pederson et al. (U.S. Pat. Nos. 7,026,495 and6,620,955, the disclosures of both of which are incorporated herein byreference) and Hoveyda et al. (U.S. Pat. No. 6,921,735 and WO0214376,the disclosures of both of which are incorporated herein by reference).

Further examples of complexes having linked ligands include those havinglinkages between a neutral NHC ligand and an anionic ligand, a neutralNHC ligand and an alkylidine ligand, a neutral NHC ligand and an L²ligand, a neutral NHC ligand and an L³ ligand, an anionic ligand and analkylidine ligand, and any combination thereof.

In addition to the catalysts that have the structure of formula (I), asdescribed above, other transition metal carbene complexes include, butare not limited to:

neutral ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 16, are penta-coordinated, and are of the general formula (IX);

neutral ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 18, are hexa-coordinated, and are of the general formula (X);

cationic ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 14, are tetra-coordinated, and are of the general formula (XI);and

cationic ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 14 or 16, are tetra-coordinated or penta-coordinated,respectively, and are of the general formula (XII)

wherein:

M, X¹, X², L¹, L², L³, R¹, and R² are as defined for any of thepreviously defined four groups of catalysts;

r and s are independently zero or 1;

t is an integer in the range of zero to 5;

k is an integer in the range of zero to 1;

Y is any non-coordinating anion (e.g., a halide ion, BF₄ ⁻, etc.);

Z¹ and Z² are independently selected from —O—, —S—, —NR²—, —PR²—,—P(═O)R²—, —P(OR²)—, —P(═O)(OR²)—, —C(═O)—, —C(═O)O—, —OC(═O)—,—OC(═O)O—, —S(═O)—, —S(═O)₂—, —, and an optionally substituted and/oroptionally heteroatom—containing C₁-C₂₀ hydrocarbylene linkage;

Z³ is any cationic moiety such as —P(R²)₃ ⁺ or —N(R²)₃ ⁺; and any two ormore of X¹, X², L¹, L², L³, Z¹, Z², Z³, R¹, and R² may be taken togetherto form a cyclic group, e.g., a multidentate ligand.

Particularly useful catalysts include:

Additional catalyst embodiments are also described in WO 2012/097379 A2,“Z-Selective Olefin Metathesis Catalysts and their Synthetic Procedure,”which is incorporated by reference herein in its entirety. Thisreference describes a series of hindered metathesis catalyst that favorthe formation of cis-bonds, and are useful for that purpose in thecontext of the present invention. These catalysts are described compoundhaving a structure of Formula (XIII),

wherein

X¹ is an anionic ligand;

L¹ is a carbene ligand having the structure of Formula (XIV):

wherein,

Q is selected from hydrocarbylene, substituted hydrocarbylene,heteroatom-containing hydrocarbylene, or substitutedheteroatom-containing hydrocarbylene, wherein two or more substituentson adjacent atoms within Q may also be linked to form an additionalcyclic structure;

R¹ is an optionally substituted hydrocarbylene or an optionallysubstituted heteroatom-containing hydrocarbylene, where R¹ links L¹ andM and, together with L¹ and M, form one or more cyclic groups, andwherein M, L¹ and R¹ form an M-R¹-L¹ chelating ligand ring structurehaving a ring size of 5, 6, or 7 atoms;

R² is an optionally substituted hydrocarbyl or an optionally substitutedheteroatom-containing hydrocarbyl’

Y is N, O, S, or P (or other two electron donor);

R³, R⁴, R⁵, and R⁶ are each, independently, hydrogen, halogen, alkyl,alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl,heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl,carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl,dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl,trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde,nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide,halogen-substituted amide, trifluoroamide, sulfide, disulfide,sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate,wherein any combination of R⁵, R⁶, R⁷, and R⁸ can be linked to form oneor more cyclic groups;

n is 1 or 2, such that n is 1 for the divalent heteroatoms O or S, and nis 2 for the trivalent heteroatoms N or P; and

Z is selected from hydrogen, alkyl, aryl, functionalized alkyl, orfunctionalized aryl wherein the functional group(s) may independentlycomprise one or more or the following: alkoxy, aryloxy, halogen,carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl,ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide,carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl,isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl andtrimethylsilyl; and wherein any combination or combinations of X¹, R¹,R², L¹, Y, Z, R³, R⁴, R⁵, and R⁶ are optionally linked to a support.

In other embodiments of Formula XIII, the methods employ hinderedruthenium metathesis catalysts of the structures above, wherein X¹ ishalide, nitrate, alkyl, aryl, alkoxy, alkylcarboxylate, aryloxy,alkoxycarbonyl, aryloxycarbonyl, arylcarboxylate, acyl, acyloxy,alkylsulfonato, arylsulfonato, alkylsulfanyl, arylsulfanyl,alkylsulfinyl, or arylsulfinyl. In other embodiments, X¹ is acarboxylate, nitrate, phenoxide, bromide, chloride, iodide, sulfoxide,or nitrite. Nitrate and pivalate ligands are particularly suitableembodiments for the methods.

In the carbene ligand having the structure of Formula (XIV), Q is alinker, typically a hydrocarbylene linker, including substitutedhydrocarbylene, heteroatom-containing hydrocarbylene, and substitutedheteroatom-containing hydrocarbylene linkers, wherein two or moresubstituents on adjacent atoms within Q may also be linked to form anadditional cyclic structure, which may be similarly substituted toprovide a fused polycyclic structure of two to about five cyclic groups.Q is often, although again not necessarily, a two-atom linkage or athree-atom linkage. In more particular embodiments, Q is a two-atomlinkage having the structure —CR¹¹R¹²—, —CR¹³R¹⁴— or CR¹¹═CR¹³,preferably —C¹¹R¹²—CR¹³R¹⁴, wherein R¹¹, R¹², R¹³ and R¹⁴ areindependently hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, or functional groups. Examples of suitable functionalgroups include carboxyl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀alkoxycarbonyl, C₅-C₂₄ alkoxycarbonyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylthio,C₅-C₂₄ arylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀ alkylsulfinyl,optionally substituted with one or more moieties selected from C₁-C₁₂alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, hydroxyl, sulfhydryl, formyl, andhalide. R¹¹, R¹², R¹³, and R¹⁴ are preferably independently selectedfrom hydrogen, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂heteroalkyl, substituted C₁-C₁₂ heteroalkyl, phenyl, and substitutedphenyl. Alternatively, any two of R¹¹, R¹², R¹³ and R¹⁴ may be linkedtogether to form a substituted or unsubstituted, saturated orunsaturated ring structure, e.g., a C₄-C₁₂ alicyclic group or a C₅ or C₆aryl group, which may itself be substituted, e.g., with linked or fusedalicyclic or aromatic groups, or with other substituents. In one furtheraspect, any one or more of R¹¹, R¹², R¹³, and R¹⁴ comprises one or moreof the linkers.

In certain embodiments, R¹ is an optionally substituted alkylene,optionally substituted heteroatom-containing alkylene, optionallysubstituted cycloalkylene, optionally substituted heteroatom-containingcycloalkylene, optionally substituted aryl, or optionally substitutedheteroaryl. In other embodiments, R¹ is an optionally substitutedcycloalkylene or optionally substituted aryl. R¹ may also be anoptionally substituted adamantylene group or a substituted C₃-C₁₂cycloalkylene group. Adamantylene is a particularly suitable R¹ moiety.

In still other embodiments of Formula XII, R¹ is an optionallysubstituted cycloalkyne, an optionally substituted heteroatom-containingcycloalkylene, an optionally substituted aryl, or an optionallysubstituted heteroaryl and R² is an optionally substituted cycloalkyl,an optionally substituted heteroatom-containing cycloalkyl, anoptionally substituted aryl, or an optionally substituted heteroaryl.Further embodiments provide that R¹ is an optionally substitutedcycloalkylene and R² is a substituted aryl group. When R² is asubstituted aryl group, certain embodiments provide that one or bothortho positions are substituted, preferably by methyl, ethyl, propyl, orisopropyl substitutents. Under these conditions, the other meta orpara-positions may also be substituted. Suitable substituent patternsinclude those where R² is 2,4,6-trimethyl phenyl (mesityl),methylisopropylphenyl (MIPP), or di-isopropylphenyl (DIPP).

In some embodiments of Formula XIII, Q is an optionally substitutedethylene (—CH₂CH₂—), R¹ is an optionally substituted adamantylene, R² is2,4,6-trimethyl phenyl (mesityl), 2-methyl, 6-isopropylphenyl (MIPP), or2,6-diisopropylphenyl (DIPP); X¹ is nitrate or pivalate, R³, R⁴, R⁵, andR⁶ are each hydrogen; Y is O; and (Z)_(n) is isopropyl.

Accordingly, suitable C—H activated olefin metathesis catalyst compoundalso comprise one or more of the following:

In general, the transition metal complexes used as catalysts herein canbe prepared by several different methods, such as those described bySchwab et al. (1996) J. Am. Chem. Soc. 118:100-110, Scholl et al. (1999)Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc.123:749-750, U.S. Pat. No. 5,312,940, and U.S. Pat. No. 5,342,909, thedisclosures of each of which are incorporated herein by reference. Alsosee U.S. Pat. Pub. No. 2003/0055262 to Grubbs et al., filed Apr. 16,2002, for “Group 8 Transition Metal Carbene Complexes asEnantioselective Olefin Metathesis Catalysts,” International PatentPublication No. WO 02/079208, and U.S. Pat. No. 6,613,910 to Grubbs etal., filed Apr. 2, 2002, for “One-Pot Synthesis of Group 8 TransitionMetal Carbene Complexes Useful as Olefin Metathesis Catalysts,” thedisclosures of each of which are incorporated herein by reference.Preferred synthetic methods are described in International PatentPublication No. WO 03/11455A1 to Grubbs et al. for “HexacoordinatedRuthenium or Osmium Metal Carbene Metathesis Catalysts,” published Feb.13, 2003, the disclosure of which is incorporated herein by reference.

Polymer Compositions

To this point, the invention has largely been described in terms ofmethods of making polymer compositions, though some aspects of theresulting polymer compositions have been described. For the sake ofclarity, however, the invention contemplates and certain embodimentsinclude those compositions that comprise at least one polymer preparedin whole or in part by any one of the inventive methods describedherein. These include, without limitation, those compositions comprisingonly a single polymer, or a plurality of individual polymer strands,whether free-standing or tethered to a substrate surface. Theseembodiments also include homopolymers and random or block co-polymersthat may or may not be capable of conducting electrons, or behaving assemiconductors, or both.

Devices

The present disclosure also contemplates those devices and portionsthereof which take advantage of the teachings presented here. That is,certain embodiments include those devices comprising one or morepolymers prepared in whole or in part by any of the methods describedherein. These include, as non-limiting examples, polymer electronicdevices (e.g. diodes, capacitors, chemical sensors, light emittingdiodes (LEDs), photodetectors, photovoltaic cells, thermoelectricdetectors, or transistors), medical implants, composite materials,antireflection coatings, antifouling coatings, microfluidics, andreactor modifications for chemical syntheses, especially, but notlimited to, those which benefit from the described advantages of thepolymer compositions which result from the methods.

The following listing of embodiments in intended to complement, ratherthan displace or supersede, the previous descriptions.

Embodiment 1. A method of metathesizing unsaturated organic compounds,said method comprising contacting at least one feedstock vapor or gascomprising at least one olefinic or acetylenic precursor with a solidtransition metal-based metathesis catalyst to form a polymer product,wherein the transition metal-based metathesis catalyst is in a solidform and the contacting is done in the absence of a liquid.

Embodiment 2. The method of Embodiment 1, wherein the olefinic oracetylenic precursor is presented to the solid transition metal-basedmetathesis catalyst as a vapor or gas.

Embodiment 3. The method of Embodiments 1 or 2, wherein the productpolymer is formed by an enyne, a diyne, or ring opening metathesispolymerization (ROMP) reaction.

Embodiment 4. The method of any one of the preceding Embodiments,wherein the olefinic or acetylenic precursor comprises a cis- ortrans-alkene or alkyne linkage.

Embodiment 5. The method of any one of the preceding Embodiments,wherein the olefinic or acetylenic precursor comprises a linearacetylenic compound.

Embodiment 6. The method of any one of the preceding Embodiments,wherein the linear acetylenic compound comprises acetylene, H—C≡C—H.

Embodiment 7. The method of any one of the preceding Embodiments, wherethe product comprises a polyacetylene polymer or polymer block.

Embodiment 8. The method of any one of the preceding Embodiments,wherein the polyacetylene comprises a cis-polyacetylene polymer orpolymer block.

Embodiment 9. The method of any one of the preceding Embodiments,wherein the polyacetylene comprises a trans-polyacetylene polymer orpolymer block.

Embodiment 10. The method of any one of the preceding Embodiments,wherein any one of the at least one feedstock comprises a singleolefinic or acetylenic precursor.

Embodiment 11. The method of any one of the preceding Embodiments,wherein any one of the at least one feedstock comprises at least twoolefinic or acetylenic precursor.

Embodiment 12. The method of any one of Embodiments 1-5 or 7-11, whereinany one of the at least one of the olefinic or acetylenic precursorscontains an electron donor substituent, such that the precursor, whenpolymerized, is capable of forming a semiconducting polymer or polymerblock that acts as an electron donor.

Embodiment 13. The method of any one of Embodiments 1-5 or 7-11, whereinany one of the at least one of the olefinic or acetylenic precursorscontains an electron acceptor substituent, such that the precursor, whenpolymerized, is capable of forming a semiconducting polymer or polymerblock that acts as an electron acceptor.

Embodiment 14. The method of any one of the preceding Embodiments,wherein two or more feedstocks are sequentially contacted with the solidtransition metal-based metathesis catalyst.

Embodiment 15. The method of any one of the preceding Embodiments,wherein the metathesis reaction is carried out under conditions wherethe at least one olefinic or acetylenic precursor has a partial pressurein a range of about 1 psia to about 200 psia.

Embodiment 16. The method of any one of the preceding Embodiments,wherein the metathesis reaction is carried out at a temperature in arange of about −10° C. to about 300° C.

Embodiment 17. The method of any one of the preceding Embodiments,further comprising depositing nanoparticles on the polymer product.

Embodiment 18. The method of any one of the preceding Embodiments,further comprising co-depositing nanoparticles during the metathesisreaction.

Embodiment 19. The method of any one of the preceding Embodiments,further comprising depositing iodine on the polymer product.

Embodiment 20. The method of any one of the preceding Embodiments,further comprising pre-reacting a second end-functionalized olefinic oracetylenic precursor with a surface, under conditions sufficient toattached the end-functionalized olefinic or acetylenic precursor to thesurface.

Embodiment 21. The method of Embodiment 20, wherein the secondend-functionalized olefinic or acetylenic precursor is attached to asurface by covalent bonding, hydrogen bonding, ionic bonding,physisorption, pi-pi interaction, Van der Waals forces, or a combinationthereof.

Embodiment 22. The method of Embodiment 20 or 21, further comprisingcontacting the attached second end-functionalized olefinic or acetylenicprecursor with the transition metal-based metathesis catalyst dissolvedin a solvent and then removing the solvent.

Embodiment 23. The method of any one of Embodiments 20 to 22, whereinthe surface is a metal, metalloid, or an inorganic or metallic oxide.

Embodiment 24. The method of any one of Embodiments 20 to 23, whereinone end of the polymer product is attached to the surface, and thepolymer product is oriented to extend from the surface, the end of thepolymer attached to the surface being the proximal end and the other endof the polymer being the distal end.

Embodiment 25. The method of Embodiment 24, wherein the transitionmetal-based metathesis catalyst is bonded to the distal end of thepolymer product.

Embodiment 26. The method of any one of Embodiments 20 to 25, whereinthe polymer product comprises a plurality of individual polymer strands,each polymer strand attached to and oriented to extend from the surface.

Embodiment 27. The method of any one of Embodiments 20 to 26 wherein thepolymer product comprises a plurality of individual polymer strandsaligned substantially parallel to one another.

Embodiment 28. The method of any one of the preceding Embodiments,wherein the transition metal-based metathesis catalyst comprises Mo, Ru,Ta, Ti, or W.

Embodiment 29. The method of any one of the preceding Embodiments,wherein the transition metal-based metathesis catalyst comprisesruthenium.

Embodiment 30. The method of any one of the preceding Embodiments,wherein the transition metal-based metathesis catalyst comprises aN-heterocyclic carbene compound of ruthenium.

Embodiment 31. The method of any one of the preceding Embodiments,wherein the transition metal-based metathesis catalyst is a Grubbs-typeruthenium catalyst.

Embodiment 32. The method of any one of the preceding Embodiments,wherein the transition metal-based metathesis catalyst is a SecondGeneration Grubbs-type ruthenium catalyst.

Embodiment 33. The method of any one of the preceding Embodiments,wherein the transition metal-based metathesis catalyst is

Embodiment 34. A method of metathesizing acetylene, according to any oneof the preceding claims, said method comprising contacting gaseousacetylene, H—C≡C—H, with a solid Second Generation Grubbs-type rutheniumcatalyst to form a polyacetylene polymer or polymer block, the interfacebetween the acetylene and the catalyst being a direct gas/solid phaseinterface.

Embodiment 35. A composition comprising at least one polymer prepared bya method of any one of the preceding Embodiments.

Embodiment 36. The composition of Embodiment 35, wherein the compositioncomprises a plurality of individual polymer strands.

Embodiment 37. The composition of Embodiment 35 or 36, wherein thecomposition is capable of conducting electrons.

Embodiment 38. The composition of any one of Embodiments 35 to 37,wherein the composition is capable of exhibiting semiconductor behavior.

Embodiment 39. A device comprising a composition of any one ofEmbodiments 35 to 38.

Embodiment 40. The device of Embodiments 39, wherein the device is adiode, capacitor, chemical sensor, light emitting diode (LED),microfluidic device, photodetector, photovoltaic cell, thermoelectricdetector, transistor, medical implant, or comprises an anti-reflectioncoatings or antifouling coating.

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees C., pressure is at ornear atmospheric.

Example 1 Materials and Methods

All glassware was oven dried and reactions were performed under ambientconditions unless otherwise noted. All solvents and reagents werepurchased from commercial suppliers and used as received unlessotherwise noted.

In the following examples, Catalyst 1 and Catalyst 2 refer to:

Example 2 Preparation of Physisorbed Films of Polyacetylene

Using a pipette, 0.5 ml of a solution of 14 mg of Catalyst 1 in 1 mLtoluene was transferred onto a glass slide. The flat-bottomed Schlenkflask containing the sample was evacuated slowly to 120 millitorr, andbackfilled with 5 psia of acetylene gas. The sample was allowed to reactat ambient room temperature for 15 hours, after which it was quenchedand rinsed with ethyl vinyl ether. Color changed from green to yellow tored to black as the polyacetylene chain length increased over severalhours. The matte black polyacetylene films produced were verified bysurface Fourier transform infrared spectroscopy.

In a second experiment, a 1.0 mg/mL solution of Catalyst 1 in acetonewas deposited onto a silicon coupon, wetting the entire surface, allwithin a “Fischer-Porter” glass pressure vessel. The acetone was slowlyremoved by evacuating the vessel at 2.0 torr. A light green film wasdeposited on the surface. The chamber was further evacuated to 100millitorr, then backfilled with 5 psia acetylene gas. The reaction wasstopped at 26 hours by evacuating the chamber. A black layer ofpolyacetylene was present on the silicon surface. The sample was cleavedunder argon for scanning electron microscopy analysis. The images showmeasured thicknesses of the polyacetylene film of approximately 700-1500nm.

Example 3 Preparation of Covalently Tethered Polyacetylene

Silicon coupons (2 cm×2 cm) were cleaned with piranha solution (70:30H₂SO₄:H₂O₂) for one hour, rinsed with DI water, methanol and acetone,and dried under argon. A monolayer of pent-5-enyl phosphonic acid wasprepared by the method described in Hanson, et al., Journal of theAmerican Chemical Society 2003, 125, 16074-16080 from a solution in THF(structure of tethered complex illustrated in FIG. 1). In anitrogen-filled glove box, the functionalized coupon was placed into asolution of 25 mg of Catalyst 2 in 2 mL of toluene, which was held understatic vacuum for 10 minutes. The coupon was removed and submerged intofresh toluene, rinsed with ˜10 mL of toluene, and allowed to dry. Thecoupon was placed in a flat-bottomed Schlenk flask, which was evacuatedto 150 millitorr and backfilled with 5 psia acetylene gas and held atambient room temperature for 16 hours. Dark black crystallites wereobserved by optical microscopy (FIG. 2). These crystallites werecontacted with a metal probe tip to provide an example of a completedevice, where the silicon substrate served as one electrode, and theprobe tip as the other.

Example 4 Demonstration of a Polyacetylene Schottky Diode

Inside of a “Fischer-Porter” glass pressure vessel, a 1.0 mg/mL solutionof Catalyst 1 in acetone was deposited onto an aluminum-coated siliconcoupon, wetting the entire surface. The acetone was slowly removed byevacuating the vessel at 2.0 torr. A light green film was deposited onthe surface. The chamber was further evacuated to 400 millitorr, thenbackfilled with 5 psia acetylene gas. The reaction was allowed toproceed at ambient room temperature and was stopped at 13 hours byevacuating the chamber. The sample was annealed at 175° C. at 200millitorr for 5 minutes, to isomerize any cis-polyacetylene totrans-polyacetylene.

A fluorine-doped tin oxide electrode (TEC 15 grade, on glass, from SigmaAldrich) was cleaned in boiling acetone. Under a blanket of argon, thiselectrode was used to make a pressure contact to the polyacetylene on Alby holding the two sides together with binder clips. See FIG. 3A for anillustration of the prepared structure Afterwards, the device was keptand characterized inside a custom-made Schlenk vessel with tungsten rodsbeaded through the glass, for use as electrodes. The connections betweeneach electrode and the tungsten rods, as well as the connections betweenthe tungsten rods and the source meter unit were made using standardwires with alligator-clips. The device was characterized using aKeithley source meter unit and custom software, while sealed at 200millitorr. The current-voltage measurement is presented in FIG. 3C. Thedata can be extrapolated to fit a non-ideal diode equation with a darkcurrent J0=1.96×10⁻⁸ A/cm2 and a diode ideality factor n=5.01. The datashowed clear evidence of rectification. See FIGS. 3B and 3C.

As those skilled in the art will appreciate, numerous modifications andvariations of the present invention are possible in light of theseteachings, and all such are contemplated hereby. For example, inaddition to the embodiments described herein, the present inventioncontemplates and claims those inventions resulting from the combinationof features of the invention cited herein and those of the cited priorart references which complement the features of the present invention.Similarly, it will be appreciated that any described material, feature,or article may be used in combination with any other material, feature,or article, and such combinations are considered within the scope ofthis invention.

The disclosures of each patent, patent application, and publicationcited or described in this document are hereby incorporated herein byreference, each in its entirety, for all purposes.

What is claimed:
 1. A method of metathesizing unsaturated organiccompounds, said method comprising contacting at least one feedstockvapor or gas comprising at least one olefinic or acetylenic precursorwith a solid transition metal-based metathesis catalyst to form apolymer product, wherein the transition metal-based metathesis catalystis in a solid form and the contacting is done in the absence of aliquid.
 2. The method of claim 1, wherein the olefinic or acetylenicprecursor is presented to the solid transition metal-based metathesiscatalyst as a gas.
 3. The method of claim 1, wherein the product polymeris formed by an enyne, a diyne, or ring opening metathesispolymerization (ROMP) reaction.
 4. The method of claim 1, wherein theolefinic or acetylenic precursor comprises a cis- or trans-alkene oralkyne linkage.
 5. The method of claim 1, wherein the olefinic oracetylenic precursor comprises a linear acetylenic compound.
 6. Themethod of claim 1, wherein the linear acetylenic compound comprisesacetylene, H—C≡C—H.
 7. The method of claim 1, where the polymer productcomprises a polyacetylene polymer or block.
 8. The method of claim 1,wherein the polymer product comprises a trans-polyacetylene polymer orblock.
 9. The method of claim 1, wherein any one of the at least onefeedstock comprises a single olefinic or acetylenic precursor.
 10. Themethod of claim 1, wherein any one of the at least one feedstockcomprises at least two olefinic or acetylenic precursor.
 11. The methodof claim 1, wherein any one of the at least one of the olefinic oracetylenic precursors contains an electron donor substituent, such thatthe precursor, when polymerized, is capable of forming a semiconductingpolymer or polymer block that acts as an electron donor.
 12. The methodof claim 1, wherein any one of the at least one of the olefinic oracetylenic precursors contains an electron acceptor substituent, suchthat the precursor, when polymerized, is capable of forming asemiconducting polymer or polymer block that acts as an electronacceptor.
 13. The method of claim 1, wherein two or more feedstocks aresequentially contacted with the solid transition metal-based metathesiscatalyst.
 14. The method of claim 1, wherein the metathesis reaction iscarried out under conditions where the at least one olefinic oracetylenic precursor has a partial pressure in a range of from about 1psia to about 200 psia.
 15. The method of claim 1, wherein themetathesis reaction is carried out at a temperature in a range of fromabout −10° C. to about 300° C.
 16. The method of claim 1, furthercomprising depositing iodine on the polymer product
 17. The method ofclaim 1, further comprising pre-reacting a second end-functionalizedolefinic or acetylenic precursor with a surface, under conditionssufficient to attached the end-functionalized olefinic or acetylenicprecursor to the surface.
 18. The method of claim 17, wherein the secondend-functionalized olefinic or acetylenic precursor is attached to asurface by covalent bonding, hydrogen bonding, ionic bonding,physisorption, pi-pi interaction, Van der Waals forces, or a combinationthereof.
 19. The method of claim 17, further comprising contacting theattached second end-functionalized olefinic or acetylenic precursor withthe transition metal-based metathesis catalyst dissolved in a solventand then removing the solvent.
 20. The method of claim 17, wherein thesurface is a metal, metalloid, or an inorganic or metallic oxide. 21.The method of claim 17, wherein one end of the polymer product isattached to the surface, and the polymer product is oriented to extendfrom the surface, the end of the polymer attached to the surface beingthe proximal end and the other end of the polymer being the distal end.22. The method of claim 24, wherein the transition metal-basedmetathesis catalyst is bonded to the distal end of the polymer product.23. The method of claim 17, wherein the polymer product comprises aplurality of individual polymer strands, each polymer strand attached toand oriented to extend from the surface.
 24. The method of claim 17,wherein the polymer product comprises a plurality of individual polymerstrands aligned substantially parallel to one another.
 25. The method ofclaim 1, wherein the transition metal-based metathesis catalyst is aGrubbs-type ruthenium catalyst.
 26. The method of claim 1, wherein thetransition metal-based metathesis catalyst is a Second GenerationGrubbs-type ruthenium catalyst.
 27. The method of claim 1, wherein thetransition metal-based metathesis catalyst is


28. The method of claim 1, said method comprising contacting gaseousacetylene, H—C≡C—H, with a solid Second Generation Grubbs-type rutheniumcatalyst to form a polyacetylene polymer or polymer block, the interfacebetween the acetylene and the catalyst being a direct gas/solid phaseinterface.
 29. A composition comprising at least one polymer prepared bythe method of claim
 1. 30. The composition of claim 29, wherein thecomposition comprises a plurality of individual polymer strands.
 31. Thecomposition of claim 29, wherein the composition is capable ofconducting electrons.
 32. The composition of claim 29, wherein thecomposition is capable of exhibiting semiconductor behavior.
 33. Adevice comprising a composition of claim
 29. 34. The device of claim 33,wherein the device is a diode, capacitor, chemical sensor, lightemitting diode (LED), microfluidic device, photodetector, photovoltaiccell, thermoelectric detector, transistor, medical implant, or comprisesan anti-reflection coatings or antifouling coating.